Electrophotographic toner

The resulting toner was loaded on a copy machine “AR-505” (commercially available from Sharp Corporation), of which fixing device was modified so that fixing can be carried out outside the machine to provide unfixed images. While sequentially raising the temperature of a fixing roller from 100° to 240° C. in an increment of 10° C., the unfixed images were subjected to a fixing test at each temperature with a fixing device (fixing speed: 390 mm/sec) of which total fixing pressure was adjusted to 40 kgf. “UNICEF Cellophane” tape (MITSUBISHI PENCIL CO., LTD., width: 18 mm, JIS Z-1522) was adhered to the fixed images, the resulting fixed images were allowed to pass through a fixing roller set at 30° C., and the tape was then removed. The optical reflective densities of the image before adhesion of the tape and after removal of the tape were measured with a reflective densitometer “RD-915” (manufactured by Macbeth Process Measurements Co.). The temperature of a fixing roller at which the ratio of the optical reflective densities (after removal of the tape/before adhesion of the tape×100) initially exceeds 90% is defined as the lowest fixing temperature. The low-temperature fixing ability was evaluated according to the following evaluation criteria. The results are shown in Table 1-2. Here, the paper used in the fixing test was CopyBond SF-70NA (75 g/m²), manufactured by Sharp Corporation.

A: Lowest fixing temperature being lower than 150° C.;
B: Lowest fixing temperature being 150° C. or higher and lower than 170° C.; and
C: Lowest fixing temperature being 170° C. or higher.

1.6 Test Example 2

A 20-ml vessel (diameter: about 3 cm) was charged with 4 g of a toner, and allowed to stand for 72 hours under environmental conditions of a temperature of 55° C. and humidity of 60%. After allowing it to stand, the extent of generation of toner aggregation was visually observed, and the storage ability was evaluated in accordance with the standard criteria. The results are shown in Table 1-2.

2.1 Production Example 1 of Resins

A: The aggregation is not found at all even after 48 hours and after 72 hours.
B: Although the aggregation is not found after 48 hours, the aggregation is slightly found after 72 hours.
C: Although the aggregation is not found after 48 hours, the aggregation is evidently found after 72 hours.
D: The aggregation is found within 48 hours.

TABLE 1-2

		Low-Temp.
	Resin Binder	Fixing	Storage
No. 1-	(Parts by Weight)	Ability	Ability

Ex. B1	Resin A/Resin B (50/50)	A	A
Ex. B2	Resin C/Resin D (50/50)	A	B
Ex. B3	Resin E	B	A
Ex. B4	Resin A/Resin F (50/50)	A	B
Ex. B5	Resin H	B	B
Comp.	Resin G	C	A
Ex. B1
Comp.	Resin F	A	D
Ex. B2

* Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that the toners of Examples 1-B1 to 1-B5 containing a polyester in which an aliphatic polyhydric alcohol having two or more secondary carbon atoms bound to hydroxyl groups is used in a proper amount have excellent storage ability and low-temperature fixing ability, as compared to those of the toners of Comparative Examples 1-B1 and 1-B2.

Example 2

Resins A to G, and I

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers other than trimellitic anhydride and an esterification catalyst, as listed in Table 2-1 or 2-2, and the contents were heated in a mantle heater to 180° C. in a nitrogen atmosphere, and thereafter heated to 230° C. over 10 hours. Thereafter, having confirmed that a conversion rate at 230° C. reached 95% or higher, the reaction mixture was cooled to 210° C., and trimellitic anhydride shown in Table 2-1 or 2-2 was supplied thereto. The mixture was subjected to a reaction at a normal pressure for 1 hour, and subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a polyester. Here, the conversion rate as used herein means a value defined by a value calculated by:
[amount of generated water in reaction/theoretical amount of generated water]×100.

2.2 Production Example 2 of Resin

Resin H

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers other than trimellitic anhydride and an esterification catalyst, as listed in Table 2-2, and the contents were heated in a mantle heater to 235° C. in a nitrogen atmosphere, and thereafter subjected to a reaction at 235° C. for 10 hours. Thereafter, the contents were subjected to a reaction at 235° C. and 8 kPa for 1 hour, then cooled to 210° C., and trimellitic anhydride shown in Table 2-2 was supplied thereto. The mixture was subjected to a reaction at a normal pressure for 1 hour, and subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a polyester.

	TABLE 2-1

	Resin A	Resin B	Resin C	Resin D	Resin E
	Amount	Amount	Amount	Amount	Amount	Resin F
	Used	Used	Used	Used	Used	Amount Used
	g	mol	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	900	10	1800	20	900	10	900	10	900	10	900	10
1,2-Propanediol	761	10	—	—	761	10	761	10	761	10	761	10
Carboxylic Acid Component
Alkenylsuccinic Anhydride (ASAN)	1072	4	1072	4	1072	4	1072	4	268	1	2144	8
Terephthalic Acid	1992	12	1992	12	2324	14	1992	12	2490	15	1328	8
Trimellitic Anhydride	576	3	576	3	384	2	576	3	576	3	576	3
Esterification Catalyst
Dibutyltin Oxide	—	—	—	—	—	—	—	—	25.0	—	—	—
Tin(II) 2-Ethylhexanoate	26.5	—	27.2	—	27.2	—	—	—	—	—	28.5	—
Titanium Compound¹⁾	—	—	—	—	—	—	26.5	—	—	—	—	—
Total Amount of Raw Material Monomers (g)	5301	5440	5441	5301	4995	5709
Amount of Alcohol A Contained in Alcohol	50.0	100.0	50.0	50.0	50.0	50.0
Component (% by mol)
Amount of ASAN Contained in Carboxylic Acid	21.1	21.1	20.0	21.1	5.3	42.1
Component (% by mol)
Alcohol A/(Raw Material Monomers Other	20.4	49.5	19.8	20.4	22.0	18.7
Than Alcohol A) × 100 (parts by weight)
Softening Point (° C.)	120.5	119.6	102.4	148.6	123.2	124.1
Glass Transition Temperature (° C.)	58.7	64.2	54.1	59.1	61.2	52.9
Acid Value (mgKOH/g)	25.3	30.4	24.6	18.4	28.4	18.4

¹⁾Titanium Diisopropylate bis(Triethanolaminate)

	TABLE 2-2

	Resin G	Resin H
	Amount	Amount	Resin I
	Used	Used	Amount Used
	g	mol	g	mol	g	mol

Raw Material
Monomers
Alcohol Component
Ethylene Glycol	620	10	—	—	620	10
Neopentyl Glycol	1040	10	—	—	1040	10
BPA-PO¹⁾	—	—	1750	5	—	—
BPA-EO²⁾	—	—	1625	5	—	—
Carboxylic Acid
Component
Alkenylsuccinic	1072	4	536	2	—	—
Anhydride A (ASAN)
Terephthalic Acid	1992	12	996	6	2324	14
Trimellitic Anhydride	576	3	288	1.5	960	5
Esterification Catalyst
Tin(II)	26.5	—	26.0	—	24.7	—
2-Ethylhexanoate
Total Amount of Raw	5300	5195	4944
Material Monomers
(g)
Amount of ASAN	21.1	21.1	0.0
Contained in
Carboxylic Acid
Component
(% by mol)
Softening Point (° C.)	115.4	118.9	116.2
Glass Transition	48.6	58.4	53.1
Temperature (° C.)
Acid Value	30.1	23.4	32.1
(mgKOH/g)

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

2.3 Examples 1 to 9 and Comparative Examples 1 to 3

One hundred parts by weight of a resin binder as shown in Table 2-3, 6 parts by weight of a cyan pigment “Toner Cyan BG” (manufactured by Clariant GmbH, C. I. Pigment 15:3), 1 part by weight of a negatively chargeable charge control agent “BONTRON S-34” (manufactured by Orient Chemical Co., Ltd.), and 2 parts by weight of a releasing agent “HNP-9” (manufactured by Nippon Seiro, melting point: 75° C.) were sufficiently mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with a unidirectional rotary twin-screw extruder at a roller rotational speed of 200 r/min and a heating temperature inside the roller of 80° C. The resulting melt-kneaded product was cooled and roughly pulverized, and thereafter pulverized with a jet mill, and a pulverized product was classified, to provide a toner particle having a volume-median particle size (D₅₀) shown in Table 2-3.

To 100 parts by weight of the resulting toner particle was added 1.0 part by weight of an external additive “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.), and the mixture was blended with a Henschel mixer, to provide each of the toners.

2.4 Example 10

The same procedures as in Example 1 were carried out except that 4 parts by weight of carbon black “MOGUL L” (manufactured by Cabot Corporation) was used in place of the cyan pigment as the colorant, to provide a toner.

2.5 Test Example 1

The same procedures as in Test Example 1 of Item 1.5 were carried out in both the test method and the evaluation criteria to evaluate low-temperature fixing ability. The results are shown in Table 2-3.

2.6 Test Example 2

Optical Density under High-Temperature, High-Humidity Conditions

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 2-3.

2.7 Test Example 3

A toner was loaded to a nonmagnetic monocomponent developer device “PAGEPRESTO N-4” (manufactured by CASIO COMPUTER CO., LTD.) provided with a stainless steel developer roller, and 500 sheets of images were continuously printed under the environmental conditions of a temperature of 40° C. and relative humidity of 90%. Optical densities for images printed at 50th sheet and at 500th sheet were measured with a transmission Macbeth densitometer “TR-927,” and a ratio of the optical densities between 50th sheet and 500th sheet, i.e. the value of optical density at 500th sheet/the value of optical density of 50th sheet), was calculated, and optical density under high-temperature, high-humidity conditions was evaluated in accordance with the following evaluation criteria. The results are shown in Table 2-3.

3.1 Production Example 1 of Resins

A: The ratio of optical densities is 0.90 or more.
B: The ratio of optical densities is 0.70 or more and less than 0.90.
C: The ratio of optical densities is less than 0.70.

	TABLE 2-3

	Evaluation of Toner
			Low-		Optical Density
			Temp.		Under High-Temp.,
			Fixing	Storage	High-Humidity
No. 2-	Resin Binder*	D₅₀	Ability	Ability	Conditions

Ex. 1	Resin A	6.8	A	A	A
Ex. 2	Resin B	6.6	B	A	A
Ex. 3	Resin C/Resin	6.7	A	B	A
	D (50/50)
Ex. 4	Resin E	6.8	A	A	B
Ex. 5	Resin F	7.1	A	B	A
Ex. 6	Resin C/Resin	6.9	A	B	B
	I (50/50)
Ex. 7	Resin C/Resin	7.1	B	B	B
	H (50/50)
Ex. 8	Resin C	6.5	A	B	A
Ex. 9	Resin D	7.1	B	A	A
Ex. 10	Resin A	6.8	A	A	A
Comp.	Resin G	6.8	A	D	B
Ex. 1
Comp.	Resin H	6.7	C	B	A
Ex. 2
Comp.	Resin I	6.7	A	D	C
Ex. 3

*Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that as compared to the toners of Examples 2-1 to 2-10, the toner of Comparative Example 2-1 containing a resin binder in which an aliphatic polyhydric alcohol other than the alcohol A is used is deficient in storage ability, even while having favorable low-temperature fixing ability, and that the toner of Comparative Example 2-2 containing a resin binder in which an aromatic polyhydric alcohol is used is deficient in low-temperature fixing ability, even while having favorable storage ability. Also, it can be seen that the toner of Comparative Example 2-3 containing a resin binder in which both the alcohol A or the succinic acid derivative is not used is deficient in storage ability and has a markedly lowered optical density under high-temperature, high humidity conditions.

Example 3

Resins A to D, F to H, and K

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractional distillation tube through which hot water at 100° C. was allowed to flow, a stirrer, and a thermocouple was charged with raw material monomers for a polyester other than trimellitic anhydride and an esterification catalyst, as listed in Tables 3-1 to 3-3. The mixture was kept at 180° C. for 1 hour in a nitrogen atmosphere, and heated from 180° to 230° C. at a rate of 10° C./hr, and the heated mixture was then subjected to a polycondensation reaction at 230° C. for 10 hours, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. After cooling the reaction mixture to 160° C., a mixture of acrylic acid (a dually reactive monomer), raw material monomers for a styrenic resin and a polymerization initiator shown in Tables 3-1 to 3-3 was added dropwise thereto with a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was matured for 1 hour, while keeping the mixture at 160° C. Thereafter, the mixture was heated to 210° C., trimellitic anhydride shown in Tables 3-1 to 3-3 was then supplied thereto, and the mixture was subjected to a reaction at 210° C. for 2 hours, and subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide a hybrid resin.

3.2 Production Example 2 of Resin

Resin E

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractional distillation tube through which hot water at 100° C. was allowed to flow, a stirrer, and a thermocouple was charged with raw material monomers for a polyester other than trimellitic anhydride and fumaric acid and an esterification catalyst, as listed in Table 3-1, and the mixture was heated to 160° C. in a nitrogen atmosphere. Thereafter, a mixture of acrylic acid (a dually reactive monomer), raw material monomers for a vinyl resin and a polymerization initiator shown in Table 3-1 was added dropwise thereto with a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was matured for 1 hour, while keeping the mixture at 160° C. Thereafter, the mixture was subjected to a polycondensation reaction at 230° C. for 10 hours, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. After cooling to 180° C., fumaric acid shown in Table 3-1 was supplied thereto, the mixture was heated from 180° C. to 210° C. at a rate of 10° C./hr, and thereafter subjected to a polycondensation reaction for 3 hours. Further, trimellitic anhydride shown in Table 3-1 was supplied thereto, and the mixture was subjected to a reaction at 210° C. for 2 hours, and subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide a hybrid resin.

3.3 Production Example 3 of Resins

Resins I, J, and L

3.4 Production Example 4 of Resin

Resin M

	TABLE 3-1

	Resin A	Resin B	Resin C	Resin D
	Amount	Amount	Amount	Amount	Resin E
	Used	Used	Used	Used	Amount Used
	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers for Polyester (PES)
Alcohol Component
2,3-Butanediol	720	8	720	8	720	8	1440	16	720	8
1,2-Propanediol	608	8	608	8	608	8	—	—	608	8
Carboxylic Acid Component
Fumaric Acid	—	—	—	—	—	—	—	—	278	2.4
Terephthalic Acid	1859	11.2	1859	11.2	1859	11.2	1859	11.2	1461	8.8
Trimellitic Anhydride	461	2.4	461	2.4	461	2.4	461	2.4	461	2.4
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	18.5	—	18.5	—	18.5	—	18.0	—	17.9	—
Dually Reactive Monomer
Acrylic Acid	60	0.96	60	0.96	60	0.96	60	0.96	60	0.96
Raw Material Monomers for Styrenic Resin (St)
Styrene	779	—	779	—	779	—	755	—	753	—
2-Ethylhexyl Acrylate	148	—	148	—	148	—	144	—	144	—
Polymerization Initiator
Dibutyl Peroxide	37	—	37	—	37	—	36	—	36	—
Amount of Alcohol A Contained in Alcohol	50	50	50	100	50
Component (% by mol)
Alcohol A/(Raw Material Monomers Other Than	24.1	24.1	24.1	60.5	25.1
Alcohol A) × 100 (parts by weight)
Total Amount of PES/Total Amount of St	4	4	4	4	4
(weight ratio)
Softening Point (° C.)	139.5	120.3	99.1	136.8	134.8
Glass Transition Temperature (° C.)	66.5	63.3	60.2	71.3	63.1
Acid Value (mgKOH/g)	33.0	49.3	56.2	30.2	54.1

	TABLE 3-2

	Resin F	Resin G	Resin H	Resin I
	Amount	Amount	Amount	Amount	Resin J
	Used	Used	Used	Used	Amount Used
	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers for Polyester (PES)
Alcohol Component
2,3-Butanediol	720	8	810	9	540	6	900	10	900	10
1,2-Propanediol	608	8	684	9	456	6	760	10	760	10
Carboxylic Acid Component
Alkenylsuccinic Anhydride A	281	1.05	—	—	—	—	—	—	—	—
Terephthalic Acid	1461	8.8	2092	12.6	1394	8.4	2324	14	2324	14
Trimellitic Anhydride	461	2.4	518	2.7	346	1.8	576	3	576	3
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	18.0	—	20.9	—	—	—	22.8	—	22.8	—
Titanium Compound¹⁾	—	—	—	—	13.5	—	—	—	—	—
Dually Reactive Monomer
Acrylic Acid	60	0.96	67	1.08	45	0.72	—	—	—	—
Raw Material Monomers for Styrenic Resin (St)
Styrene	754	—	377	—	1507	—	—	—	—	—
2-Ethylhexyl Acrylate	144	—	72	—	287	—	—	—	—	—
Polymerization Initiator
Dibutyl Peroxide	36	—	18	—	72	—	—	—	—	—
Amount of 2,3-BD Contained in Alcohol	50	50	50	50	50
Component (% by mol)
Alcohol A/(Raw Material Monomers Other Than	25.1	24.1	24.1	24.6	24.6
Alcohol A) × 100 (parts by weight)
Total Amount of PES/Total Amount of St	4	9	1.5	0	0
(weight ratio)
Softening Point (° C.)	136.1	138.3	137.3	140.5	97.5
Glass Transition Temperature (° C.)	61.9	68.3	62.6	75.0	59.6
Acid Value (mgKOH/g)	48.5	38.2	30.1	32.4	56.1

¹⁾Titanium Diisopropylate bis(Triethanolaminate)

	TABLE 3-3

	Resin K	Resin L
	Amount	Amount	Resin M
	Used	Used	Amount Used
	g	mol	g	mol	g	mol

Raw Material
Monomers for
Polyester (PES)
Alcohol Component
Ethylene Glycol	595	9.6	893	14.4	—	—
Neopentyl Glycol	666	6.4	998	9.6	—	—
BPA-PO¹⁾	—	—	—	—	2450	7
BPA-EO²⁾	—	—	—	—	975	3
Carboxylic Acid
Component
Terephthalic Acid	1726	10.4	2590	15.6	1079	6.5
Trimellitic Anhydride	614	3.2	922	4.8	384	2
Esterification Catalyst
Tin(II)	18.1	—	27.0	—	24.4	—
2-Ethylhexanoate
Dually Reactive
Monomer
Acrylic Acid	26	0.42	—	—	—	—
Raw Material
Monomers for Styrenic
Resin (St)
Styrene	762	—	—	—	—	—
2-Ethylhexyl Acrylate	145	—	—	—	—	—
Polymerization
Initiator
Dibutyl Peroxide	36	—	—	—	—	—
Total Amount of PES/	4	0	0
Total Amount of St
(weight ratio)
Softening Point (° C.)	123.1	122.5	119.6
Glass Transition	57.5	59.4	62.1
Temperature (° C.)
Acid Value	43.2	41.0	24.6
(mgKOH/g)

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

3.5 Examples 1 to 11 and Comparative Examples 1 to 3

One hundred parts by weight of a resin binder as shown in Table 3-4, 4 parts by weight of a carbon black “MOGUL L” (manufactured by Cabot Corporation), 1 part by weight of a negatively chargeable charge control agent “BONTRON S-34” (manufactured by Orient Chemical Co., Ltd.), and 2 part by weight of a polypropylene wax “NP-105” (manufactured by MITSUI CHEMICALS, INC.: melting point 140° C.) were sufficiently mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with a unidirectional rotary twin-screw extruder at a roller rotational speed of 200 r/min and a heating temperature inside the roller of 80° C. The resulting melt-kneaded product was cooled and roughly pulverized, and thereafter pulverized with a jet mill, and a pulverized product was classified, to provide a toner particle having a volume-median particle size (D₅₀) of 8.0 μM.

3.6 Test Example 1

3.7 Test Example 2

Triboelectric Stability under High-Temperature, High-Humidity Conditions

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 3-4.

3.8 Test Example 3

A 50 ml polyethylene bottle was charged with 0.6 g of a toner and 19.4 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo, average particle size: 90 μm) at a temperature of 32° C. and relative humidity of 85%, and the contents were mixed with a ball-mill at a rate of 250 r/min, and triboelectric charges of the toner were determined with a Q/M meter (manufactured by EPPING).

After a given period of mixing time, a mixture of a toner and a carrier in defined amounts was supplied into a cell provided in the Q/M meter, and only the toner was aspirated for 90 seconds through a sieve having a sieve opening of 32 μm (made of stainless steel, twilled, wire diameter: 0.0035 mm). The voltage change generated on the carrier at this time was monitored and the value of [Total Electric Charges (μC) After 90 Seconds/Weight (g) of Toner Aspirated] was obtained as triboelectric charges (μC/g). A ratio of triboelectric charges after a 60-second mixing time to triboelectric charges after a 600-second mixing time, i.e. triboelectric charges after 60-second mixing time/triboelectric charges after 600-second mixing time, were calculated, and triboelectric stability was evaluated in accordance with the following criteria. The results are shown in Table 3-4.

4.1 Production Example 1 of Crystalline Polyesters

A: 0.8 or more
B: 0.6 or more and less than 0.8
C: less than 0.6

	TABLE 3-4

	Evaluation of Toner
				Triboelectric
				Stability
		Low-		Under High-
		Temp.		Temperature,
		Fixing	Storage	High-Humidity
No. 3-	Resin Binder*	Ability	Ability	Conditions

Ex. 1	Resin A/Resin C (50/50)	A	A	A
Ex. 2	Resin B	B	A	A
Ex. 3	Resin D/Resin C (50/50)	A	A	A
Ex. 4	Resin E/Resin C (50/50)	A	B	A
Ex. 5	Resin F/Resin C (50/50)	A	B	A
Ex. 6	Resin G/Resin C (50/50)	A	A	B
Ex. 7	Resin H/Resin C (50/50)	A	B	A
Ex. 8	Resin I/Resin C (50/50)	A	A	B
Ex. 9	Resin A/Resin J (50/50)	A	B	B
Ex. 10	Resin A	B	A	A
Ex. 11	Resin C	A	B	A
Comp.	Resin K	A	D	B
Ex. 1
Comp.	Resin L	A	D	C
Ex. 2
Comp.	Resin M	C	B	C
Ex. 3

*Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that as compared to the toners of Examples 3-1 to 3-11, the toner of Comparative Example 3-1 containing a resin binder in which an aliphatic polyhydric alcohol other than the alcohol A is used is deficient in storage ability, even while having favorable low-temperature fixing ability, and that the toner of Comparative Example 3-2 containing as a resin binder only a polycondensation resin in which an aliphatic polyhydric alcohol other than the alcohol A is used is deficient in storage ability and triboelectric stability under high-temperature, high humidity conditions, even while having favorable low-temperature fixing ability. Also, it can be seen that the toner of Comparative Example 3-3 containing as a resin binder only a polycondensation resin in which an aromatic polyhydric alcohol is used is deficient in all of low-temperature fixing ability, storage ability and triboelectric stability under high-temperature, high humidity conditions.

Example 4

Resins A, B, and D to F

A 5-liter four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride, an esterification catalyst and a polymerization inhibitor, as listed in Table 4-1. The mixture was subjected to a reaction at 160° C. over 5 hours, and thereafter heated to 200° C. Further, trimellitic anhydride shown in Table 4-1 was supplied thereto, and the mixture was subjected to a reaction for 20 minutes, to provide a crystalline polyester.

4.2 Production Example 2 of Crystalline Polyester

4.3 Production Example 1 of Amorphous Polyesters

A 5-liter four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride and an esterification catalyst, as listed in Table 4-1. The mixture was subjected to a reaction at 180° C. over 5 hours, and thereafter heated to 200° C. Further, trimellitic anhydride shown in Table 4-1 was supplied thereto, and the mixture was subjected to a reaction at the same temperature for 20 minutes, to provide a crystalline polyester.

Resins G and H

A 5-liter four-neck flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractional distillation tube through which hot water at 100° C. was allowed to flow, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride and an esterification catalyst, as listed in Table 4-2. The mixture was kept at 180° C. for 1 hour in a nitrogen atmosphere, heated at from 180° C. to 230° C. at a rate of 10° C./hr, and thereafter subjected to a polycondensation reaction at 230° C. for 10 hours. Further, trimellitic anhydride shown in Table 4-2 was supplied thereto, and the mixture was subjected to a reaction at the same temperature and 10 kPa until a desired softening point was reached, to provide an amorphous polyester.

4.4 Production Example 2 of Amorphous Polyester

Resin I

A 5-liter four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride, an esterification catalyst, and a polymerization inhibitor, as listed in Table 4-2. The mixture was subjected to a reaction at 180° C. over 5 hours, and thereafter heated to 210° C. at a rate of 10° C./hr. Thereafter, the mixture was subjected to a reaction at 8.3 kPa for 1 hour. Further, trimellitic anhydride shown in Table 4-2 was supplied thereto, and the mixture was subjected to a reaction at the same temperature and 10 kPa until a desired softening point was reached, to provide an amorphous polyester.

	TABLE 4-1

	Resin A	Resin B	Resin C	Resin D	Resin E
	Amount	Amount	Amount	Amount	Amount	Resin F
	Used	Used	Used	Used	Used	Amount Used
Crystalline Polyester	g	mol	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	180	2	540	6	144	1.6	180	2	180	2	—	—
1,6-Hexanediol	2124	18	1652	14	1699	14.4	2124	18	2124	18	2360	20
Carboxylic Acid Component
Fumaric Acid	2088	18	2088	18	—	—	1972	17	2320	20	1670	14.4
Alkenylsuccinic Anhydride A	—	—	—	—	—	—	268	1	—	—	—	—
Terephthalic Acid	—	—	—	—	2390	14.4	—	—	—	—	—	—
Trimellitic Anhydride	192	1	192	1	154	0.8	192	1	—	—	192	1
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	22.9	—	22.4	—	21.9	—	23.7	—	23.1	—	21.1	—
Polymerization Inhibitor
tert-Butyl Catechol	2.3	—	2.2	—	—	—	2.4	—	2.3	—	2.1	—
Total Amount of Raw Material Monomers (g)	4584	4472	4387	4736	4624	4222
Amount of Alcohol A Contained in Alcohol	10	30	10	10	10	0
Component (% by mol)
Alcohol A/(Raw Material Monomers Other Than	4.1	13.7	3.4	4.0	4.1	0
Alcohol A) × 100 (parts by weight)
Softening Point (° C.)	117.2	115.4	125.2	112.5	117.5	111.6
Temperature of Maximum Endothermic Peak	104.3	99.6	135.2	100.5	111.2	113.5
(° C.)
Softening Point/Temperature of Maximum	1.12	1.16	0.93	1.12	1.06	0.98
Endothermic Peak

	TABLE 4-2

	Resin G	Resin H
	Amount	Amount	Resin I
	Used	Used	Amount Used
Amorphous Polyester	g	mol	g	mol	g	mol

Raw Material
Monomers
Alcohol Component
2,3-Butanediol	1800	20	—	—	—	—
Ethylene Glycol	—	—	744	12	—	—
Neopentyl Glycol	—	—	832	8	—	—
BPA-PO¹⁾	—	—	—	—	2450	7
BPA-EO²⁾	—	—	—	—	975	3
Carboxylic Acid
Component
Fumaric Acid	—	—	—	—	870	7.5
Terephthalic Acid	2158	13	2158	13	—	—
Trimellitic Anhydride	768	4	768	4	480	2.5
Esterification Catalyst
Tin(II)	23.6	—	22.5	—	23.9	—
2-Ethylhexanoate
Polymerization
Inhibitor
tert-Butyl Catechol	—	—	—	—	2.4	—
Total Amount of Raw	4726	4502	4775
Material Monomers
(g)
Amount of Alcohol A	100	0	0
Contained in Alcohol
Component
(% by mol)
Alcohol A/(Raw	61.5	0	0
Material Monomers
Other Than Alcohol
A) × 100
(parts by weight)
Softening Point (° C.)	136.1	138.6	140
Temperature of	38.4	35.7	28.7
Maximum
Endothermic
Peak (° C.)
Softening Point/	3.54	3.88	4.88
Temperature of
Maximum
Endothermic Peak
Glass Transition	73.5	63.2	62.1
Temperature (° C.)
Acid Value	32.4	43.2	24.6
(mgKOH/g)

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

4.5 Examples 1 to 8 and Comparative Examples 1 and 2

One hundred parts by weight of a resin binder as shown in Table 4-3, 4 parts by weight of a carbon black “MOGUL L” (manufactured by Cabot Corporation), 1 part by weight of a negatively chargeable charge control agent “BONTRON S-34” (manufactured by Orient Chemical Co., Ltd.), and 2 parts by weight of a polypropylene wax “NP-105” (manufactured by MITSUI CHEMICALS, INC., melting point: 140° C.) were sufficiently mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with a unidirectional rotary twin-screw extruder at a roller rotational speed of 200 r/min and a heating temperature inside the roller of 80° C. The resulting melt-kneaded product was cooled and roughly pulverized, and thereafter pulverized with a jet mill, and a pulverized product was classified, to provide a toner particle having a volume-median particle size (D₅₀) of 8.0 μm.

4.6 Test Example 1

The same procedures as in Test Example 1 of Item 1.5 were carried out in the test method to evaluate low-temperature fixing ability, provided that the evaluation criteria are as follows. The results are shown in Table 4-3.

A: The lowest fixing temperature is less than 140° C.
B: The lowest fixing temperature is 140° C. or more and less than 150° C.
C: The lowest fixing temperature is 150° C. or more and less than 170° C.
D: The lowest fixing temperature is 170° C. or more.

4.7 Test Example 2

5.1 Production Example 1 of Resins

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 4-3.

	TABLE 4-3

	Evaluation of Toner
		Low-Temperature	Storage
No. 4-	Resin Binder*	Fixing Ability	Ability

Ex. 1	Resin A/Resin G (20/80)	A	A
Ex. 2	Resin A/Resin H (20/80)	A	B
Ex. 3	Resin A/Resin I (20/80)	B	B
Ex. 4	Resin B/Resin G (20/80)	B	A
Ex. 5	Resin C/Resin G (20/80)	B	A
Ex. 6	Resin D/Resin G (20/80)	A	B
Ex. 7	Resin E/Resin G (20/80)	A	B
Ex. 8	Resin F/Resin G (20/80)	A	B
Comp.	Resin F/Resin H (20/80)	B	D
Ex. 1
Comp.	Resin F/Resin I (20/80)	D	D
Ex. 2

*Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that as compared to the toners of Comparative Examples 4-1 and 4-2, the toners of Examples 4-1 to 4-8 in which at least either one of the amorphous polyester and the crystalline polyester contains an alcohol A as a resin binder have both favorable low-temperature fixing ability and storage ability. Also, when storage ability of Examples 4-6 to 4-8 is compared, storage ability is in the same rank B, with Examples 4-6 and 4-7 being slightly more excellent.

Example 5

Resins A to G, and J

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractional distillation tube through which hot water at 100° C. was allowed to flow, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride, an esterification catalyst and pyrogallic acid, as listed in Table 5-1 or 5-2. The mixture was kept at 180° C. for 1 hour in a nitrogen atmosphere, and heated from 180° to 230° C. at a rate of 10° C./hr, and thereafter the mixture was subjected to a polycondensation reaction at 230° C. for 10 hours, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. After cooling the reaction mixture to 210° C., trimellitic anhydride shown in Table 5-1 or 5-2 was supplied thereto, and then the mixture was subjected to a reaction at 210° C. for 2 hours, and subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide a polyester. Here, pyrogallic acid was not used in Resins G and J.

5.2 Production Example 2 of Resin

Resin H

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractional distillation tube through which hot water at 100° C. was allowed to flow, a stirrer, and a thermocouple was charged with raw material monomers for a polyester other than trimellitic anhydride, an esterification catalyst, and pyrogallic acid, as listed in Table 5-2. The mixture was kept at 180° C. for 1 hour in a nitrogen atmosphere, and heated from 180° to 230° C. at a rate of 10° C./hr, and thereafter the heated mixture was subjected to a polycondensation reaction at 230° C. for 10 hours, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. After cooling the reaction mixture to 160° C., a mixture of a dually reactive monomer (acrylic acid), raw material monomers for a vinyl resin, and a polymerization initiator as listed in Table 5-2 was added dropwise thereto with a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was matured for 1 hour, while keeping the mixture at 160° C. Thereafter, the mixture was heated to 210° C., trimellitic anhydride shown in Table 5-2 was then supplied thereto, and the mixture was subjected to a reaction at 210° C. for 2 hours, and subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide a hybrid resin.

5.3 Production Example 3 of Resin

Resin I

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride, an esterification catalyst, pyrogallic acid and a polymerization inhibitor (tert-butyl catechol), as listed in Table 5-2. The mixture was subjected to a reaction at 160° C. over 5 hours, and then heated to 200° C. Further, trimellitic anhydride shown in Table 5-2 was supplied thereto, and the mixture was subjected to a reaction for 20 minutes, to provide a crystalline polyester. Resin I had a temperature of maximum endothermic peak of 112.8° C.

5.4 Production Example 4 of Resin

Resin K

A 5-liter four neck flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride and an esterification catalyst, as listed in Table 5-2. The mixture was subjected to a polycondensation reaction at 230° C. for 10 hours in a nitrogen atmosphere, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. Further, trimellitic anhydride shown in Table 5-2 was subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide a polyester.

	TABLE 5-1

	Resin A	Resin B	Resin C	Resin D	Resin E	Resin F
	Amount	Amount	Amount	Amount	Amount	Amount	Resin G
	Used	Used	Used	Used	Used	Used	Amount
	g	mol	g	mol	g	mol	g	mol	g	mol	g	mol	Used

Raw Material Monomers
Alcohol Component
2,3-Butanediol	900	10	900	10	900	10	1800	20	900	10	900	10	900	10
1,2-Propanediol	760	10	760	10	760	10	0	0	760	10	760	10	760	10
Carboxylic Acid Component
Alkenylsuccinic Anhydride A	—	—	—	—	—	—	—	—	804	3	—	—	—	—
Terephthalic Acid	2324	14	2324	14	1992	12	2324	14	1826	11	2324	14	2324	14
Trimellitic Anhydride	576	3	576	3	576	3	576	3	576	3	576	3	576	3
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	22.8	—	22.8	—	21.1	—	23.5	—	24.3	—	—	—	22.8	—
Titanium Compound¹⁾	—	—	—	—	—	—	—	—	—	—	22.8	—	—	—
Pyrogallic Acid	2.3	—	2.3	—	2.1	—	2.4	—	2.4	—	2.3	—	—	—
Amount of Alcohol A Contained in	50	50	50	100	50	50	50
Alcohol Component (% by mol)
Alcohol A/(Raw Material	24.6	24.6	27.0	62.1	22.7	24.6	24.6
Monomers Other Than Alcohol
A) × 100 (parts by weight)
Softening Point (° C.)	139.5	120.3	99.1	136.8	134.8	136.1	138.3
Glass Transition Temperature	70.3	65.3	63.2	74.2	63.1	67.8	67.5
(° C.)
Acid Value (mgKOH/g)	33.0	42.1	30.2	30.2	27.4	38.5	35.9

¹⁾Titanium Diisopropylate bis(Triethanolaminate)

	TABLE 5-2

	Resin H	Resin I	Resin J	Resin K
	Amount	Amount	Amount	Amount
	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	720	8	180	2	—	—	—	—
1,2-Propanediol	608	8	—	—	—	—	—	—
1,6-Hexanediol	—	—	2124	18	—	—	—	—
Ethylene Glycol	—	—	—	—	744	12	—	—
Neopentyl Glycol	—	—	—	—	832	8	—	—
BPA-PO¹⁾	—	—	—	—	—	—	2450	7
BPA-EO²⁾	—	—	—	—	—	—	975	3
Carboxylic Acid Component
Fumaric Acid	—	—	2088	18	—	—	—	—
Terephthalic Acid	1859	11.2	—	—	2158	13	1079	6.5
Trimellitic Anhydride	461	2.4	192	1	768	4	384	2
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	18.5	—	22.9	—	22.5	—	24.4	—
Pyrogallic Acid	1.9	—	2.3	—	—	—	—	—
Polymerization Inhibitor
tert-Butyl Catechol	—	—	2.3	—	—	—	—	—
Dually Reactive Monomer
Acrylic Acid	60	0.96	—	—	—	—	—	—
Raw Material Monomers for Vinyl Resin
Styrene	779	—	—	—	—	—	—	—
2-Etylhexyl Acrylate	148	—	—	—	—	—	—	—
Polymerization Initiator
Dibutyl Peroxide	37	—	—	—	—	—	—	—
Amount of Alcohol A Contained in	50	10	0	0
Alcohol Component (% by mol)
Alcohol A/(Raw Material Monomers	24.1	7.9	0	0
Other Than Alcohol A) × 100
(parts by weight)
Softening Point (° C.)	136.1	113.5	122.5	124.3
Glass Transition Temperature (° C.)	61.9	—	60.2	62.1
Acid Value (mgKOH/g)	48.5	—	46.9	24.6

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

5.5 Examples 1 to 7 and Comparative Examples 1 to 3

One hundred parts by weight of a resin binder as shown in Table 5-3, 4 parts by weight of a carbon black “MOGUL L” (manufactured by Cabot Corporation), 1 part by weight of a negatively chargeable charge control agent “BONTRON S-34” (manufactured by Orient Chemical Co., Ltd.), and 2 parts by weight of a polypropylene wax “NP-105” (manufactured by MITSUI CHEMICALS, INC., melting point: 140° C.) were sufficiently mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with a unidirectional rotary twin-screw extruder at a roller rotational speed of 200 r/min and a heating temperature inside the roller of 80° C. The resulting melt-kneaded product was cooled and roughly pulverized, and thereafter pulverized with a jet mill, and a pulverized product was classified, to provide a toner particle having a volume-median particle size (D₅₀) of 8.0 μm.

5.6 Test Example 1

5.7 Test Example 2

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 5-3.

5.8 Test Example 3

Durability

A toner was loaded to a printer “PAGEPRESTO N-4” (manufactured by CASIO COMPUTER CO., LTD., fixing: contact-fixing method, development method: nonmagnetic monocomponent development method, diameter of developer roller: 2.3 cm), and printing was conducted continuously on obliquely striped patterns having a print coverage of 5.5% under the environmental conditions of 32° C. and humidity of 85%. During the course of printing, black solid images were printed for every 500 sheets, and the presence or absence of the lines on the formed images was confirmed. At the point where the generation of the lines was confirmed, printing was stopped. The test was conducted up to 5,000 sheets at the maximum. Durability was evaluated by defining the number of printed sheets at the point where the generation of lines was visually confirmed on the images as the number of sheets at which lines were generated by fusion or fixing of toner on a developer roller, in accordance with the following evaluation criteria. In other words, it can be judged that the larger the number of sheets without generation of lines, the higher the durability of toner. The results are shown in Table 5-3.

6.1 Production Example 1 of Amorphous Hybrid Resins

A: No lines are generated up until printing 5,000 sheets.
B: Lines are generated on printing 2,000 sheets or more and less than 5,000 sheets.
C: Lines are generated on printing less than 2,000 sheets.

	TABLE 5-3

	Evaluation of Toner
		Low-Temp.	Storage
No. 5-	Resin Binder*	Fixing Ability	Ability	Durability

Ex. 1	Resin A/Resin C (50/50)	A	A	A
Ex. 2	Resin B	A	A	B
Ex. 3	Resin D/Resin C (50/50)	A	A	A
Ex. 4	Resin E/Resin C (50/50)	A	A	A
Ex. 5	Resin F/Resin C (50/50)	A	A	B
Ex. 6	Resin H/Resin C (50/50)	A	A	A
Ex. 7	Resin A/Resin I (80/20)	A	B	B
Comp.	Resin J	A	D	B
Ex. 1
Comp.	Resin K	C	B	B
Ex. 2
Comp.	Resin G/Resin J (50/50)	A	B	C
Ex. 3

*Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that as compared to the toners of Examples 5-1 to 5-7, the toner of Comparative Example 5-1 containing a resin binder in which an aliphatic polyhydric alcohol other than the alcohol A is used is deficient in storage ability and durability, even while having favorable low-temperature fixing ability, and that the toner of Comparative Example 5-2 containing a resin binder in which an aromatic polyhydric alcohol is used has markedly lowered low-temperature fixing ability and durability. Also, it can be seen that the toner of Comparative Example 5-3 in which a resin using a pyrogallol compound is used together is deficient in durability.

Example 6

Resins H1, H2, and H3

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractional distillation tube through which hot water at 100° C. was allowed to flow, a stirrer, and a thermocouple was charged with raw material monomers for a polyester other than trimellitic anhydride and an esterification catalyst, as listed in Table 6-1. The mixture was kept at 180° C. for 1 hour in a nitrogen atmosphere, and heated from 180° to 230° C. at a rate of 10° C./hr, and the heated mixture was then subjected to a polycondensation reaction at 230° C. for 10 hours, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. After cooling the reaction mixture to 160° C., a mixture of acrylic acid (a dually reactive monomer), raw material monomers for a styrenic resin, and a polymerization initiator, as listed in Table 6-1 was added dropwise thereto with a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was matured for 1 hour, while keeping the mixture at 160° C. Thereafter, the mixture was heated to 210° C., trimellitic anhydride shown in Table 6-1 was then supplied thereto, and the mixture was subjected to a reaction at 210° C. for 2 hours, and subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide an amorphous hybrid resin.

6.2 Production Example 2 of Amorphous Hybrid Resin

Resin H4

A 5-liter four neck flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple was charged with raw material monomers for a polyester other than trimellitic anhydride and an esterification catalyst, as listed in Table 6-1. The mixture was heated to 160° C. in a nitrogen atmosphere. Thereafter, a mixture of acrylic acid (a dually reactive monomer), raw material monomers for a vinyl resin, and a polymerization initiator, as listed in Table 6-1 was added dropwise thereto with a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was matured for 1 hour, while keeping the mixture at 160° C. Thereafter, the mixture was subjected to a polycondensation reaction at 230° C. for 10 hours, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. Further, trimellitic anhydride shown in Table 6-1 was supplied thereto, and the mixture was subjected to a reaction at 210° C. for 2 hours, and subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide an amorphous hybrid resin.

6.3 Production Example 1 of Amorphous Polyesters

Resins A1, A2, and A4

6.4 Production Example 2 of Amorphous Polyesters

Resins A3 and A5

6.5 Production Example 1 of Crystalline Polyesters

Resins C1 and C2

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with raw material monomers other than trimellitic anhydride, an esterification catalyst, and a polymerization inhibitor, as listed in Table 6-3. The mixture was subjected to a reaction at 160° C. over 5 hours, and heated to 200° C. Further, trimellitic anhydride shown in Table 6-3 was supplied thereto, and the mixture was subjected to a reaction for 20 minutes, to provide a crystalline polyester.

	TABLE 6-1

	Resin H1	Resin H2	Resin H3	Resin H4
	Amount	Amount	Amount	Amount
	Used	Used	Used	Used
Amorphous Hybrid Resin	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers for Polyester (PES)
Alcohol Component
2,3-Butanediol	720	8	720	8	—	—	—	—
1,2-Propanediol	608	8	608	8	—	—	—	—
Ethylene Glycol	—	—	—	—	595	9.6	—	—
Neopentyl Glycol	—	—	—	—	666	6.4	—	—
1,6-Hexanediol	—	—	—	—	—	—	—	—
BPA-PO¹⁾	—	—	—	—	—	—	1715	4.9
BPA-EO²⁾	—	—	—	—	—	—	683	2.1
Carboxylic Acid Component
Alkenylsuccinic Anhydride A (ASAN)	—	—	643	2.4	—	—	—	—
Terephthalic Acid	1859	11.2	1461	8.8	1726	10.4	755	4.55
Trimellitic Anhydride	461	2.4	461	2.4	614	3.2	269	1.4
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	18.5	—	19.8	—	18.1	—	17.2	—
Dually Reactive Monomer
Acrylic Acid	60	0.96	60	0.96	26	0.42	26	0.42
Raw Material Monomers for Styrenic Resin (St)
Styrene	779	—	830	—	762	—	724	—
2-Etylhexyl Acrylate	148	—	158	—	145	—	138	—
Polymerization Initiator
Dibutyl Peroxide	37	—	40	—	36	—	34	—
Amount of Alcohol A Contained in Alcohol	50	50	0	0
Component (% by mol)
Alcohol A/(Raw Material Monomers Other	24.6	22.7	0	0
Than Alcohol A) × 100 (parts by weight)
Amount of ASAN Contained in Carboxylic	0	17.6	0	0
Acid Component (% by mol)
Total Amount of PES/Total Amount of St	4	4	4	4
(weight ratio)
Softening Point (° C.)	139.5	136.1	140.3	134.9
Temperature of Maximum	70.4	66.7	64.2	66.1
Endothermic Peak (° C.)
Softening Point/Temperature of Maximum	2.0	2.0	2.2	2.0
Endothermic Peak
Glass Transition Temperature (° C.)	66.5	61.9	59.6	62.1
Acid Value (mgKOH/g)	33	48.5	33.5	20.3
Hydroxyl Value (mgKOH/g)	30.1	38.4	29.6	22.4

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

	TABLE 6-2

	Resin A1	Resin A2	Resin A3	Resin A4	Resin A5
	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used
Amorphous Polyester	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	720	8	—	—	—	—	—	—	—	—
1,2-Propanediol	608	8	—	—	—	—	—	—	—	—
Ethylene Glycol	—	—	595	9.6	—	—	744	12	—	—
Neopentyl Glycol	—	—	666	6.4	—	—	832	8	—	—
BPA-PO¹⁾	—	—	—	—	1715	4.9	—	—	2450	7
BPA-EO²⁾	—	—	—	—	683	2.1	—	—	975	3
Carboxylic Acid Component
Alkenylsuccinic Anhydride A (ASAN)	858	3.2	643	2.4	281	1.05	—	—	—	—
Terephthalic Acid	1328	8	1328	8	581	3.5	2158	13	1079	6.5
Trimellitic Anhydride	461	2.4	614	3.2	269	1.4	768	4	384	2
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	19.9	—	19.2	—	17.6	—	22.5	—	24.4	—
Amount of Alcohol A Contained in	50	0	0	0	0
Alcohol Component (% by mol)
Alcohol A/(Raw Material Monomers	22.0	0	0	0	0
Other Than Alcohol A) × 100
(parts by weight)
Amount of ASAN Contained in	23.5	17.6	17.6	0	0
Carboxylic Acid Component (% by mol)
Softening Point (° C.)	136.8	136.5	134.9	130.2	135.6
Temperature of Maximum Endothermic	68.5	60.9	65.3	66.1	68.1
Peak (° C.)
Softening Point/Temperature of	2.0	2.2	2.1	2.0	2.0
Maximum Endothermic Peak
Glass Transition Temperature (° C.)	61.6	56.3	62.1	62.1	64.2
Acid Value (mgKOH/g)	30.2	29.4	20.3	35	24.6
Hydroxyl Value (mgKOH/g)	43.2	25.6	22.4	45.2	21.2

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

	TABLE 6-3

	Resin C1	Resin C2
	Amount Used	Amount Used
Crystalline Polyester	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	180	2	—	—
1,6-Hexanediol	2124	18	2360	20
Carboxylic Acid Component
Fumaric Acid	2088	18	2088	18
Trimellitic Anhydride	192	1	192	1
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	22.9	—	23.2	—
Polymerization Inhibitor
tert-Butyl Catechol	2.3	—	2.3	—
Amount of Alcohol A Contained in	10	0
Alcohol Component (% by mol)
Alcohol A/(Raw Material Monomers	7.9	0
Other Than Alcohol A) × 100
(parts by weight)
Softening Point (° C.)	117.2	111.6
Temperature of Maximum Endothermic	104.3	113.5
Peak (° C.)
Softening Point/Temperature of	1.12	0.98
Maximum Endothermic Peak

6.6 Examples 1 to 13 and Comparative Examples 1 to 6

One hundred parts by weight of a resin binder as shown in Table 6-4, 4 parts by weight of a carbon black “MOGUL L” (manufactured by Cabot Corporation), 1 part by weight of a negatively chargeable charge control agent “BONTRON S-34” (manufactured by Orient Chemical Co., Ltd.), and 2 parts by weight of a polypropylene wax “NP-105” (manufactured by MITSUI CHEMICALS, INC., melting point: 140° C.) were sufficiently mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with a unidirectional rotary twin-screw extruder at a roller rotational speed of 200 r/min and a heating temperature inside the roller of 80° C. The resulting melt-kneaded product was cooled and roughly pulverized, and thereafter pulverized with a jet mill, and a pulverized product was classified, to provide a toner particle having a volume-median particle size (D₅₀) of 8.0 μm.

6.7 Test Example 1

The same procedures as in Test Example 1 of Item 1.5 were carried out in both the test method and the evaluation criteria to evaluate low-temperature fixing ability, provided that the evaluation criteria are as follows. The results are shown in Table 6-4.

A: The lowest fixing temperature is less than 140° C.
B: The lowest fixing temperature is 140° C. or more and less than 150° C.
C: The lowest fixing temperature is 150° C. or more and less than 170° C.
D: The lowest fixing temperature is 170° C. or more.

6.8 Test Example 2

Triboelectric Stability under High-Temperature, High-Humidity Conditions

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 6-4.

6.9 Test Example 3

7.1 Production Example 1 of Resins

A: 0.9 or more
B: 0.6 or more and less than 0.9
C: less than 0.6

	TABLE 6-4

	Evaluation of Toner
				Triboelectric Stability
		Low-Temp.	Storage	Under High-Temperature,
No. 6-	Resin Binder*	Fixing Ability	Ability	High-Humidity Conditions

Ex. 1	Resin H1/Resin C1 (80/20)	A	A	A
Ex. 2	Resin H1/Resin C2 (80/20)	A	B	A
Ex. 3	Resin H2/Resin C2 (80/20)	A	B	A
Ex. 4	Resin A1/Resin C1 (80/20)	A	A	B
Ex. 5	Resin A1/Resin C2 (80/20)	A	B	B
Ex. 6	Resin H3/Resin C1 (80/20)	A	B	A
Ex. 7	Resin H4/Resin C1 (80/20)	B	B	A
Ex. 8	Resin A2/Resin C1 (80/20)	A	B	B
Ex. 9	Resin A3/Resin C1 (80/20)	B	B	B
Ex. 10	Resin H1/Resin A1/Resin C1 (40/40/20)	A	A	A
Ex. 11	Resin H1/Resin A1/Resin C2 (40/40/20)	A	B	A
Ex. 12	Resin H1/Resin A2/Resin C1 (40/40/20)	A	B	B
Ex. 13	Resin H3/Resin A1/Resin C1 (40/40/20)	A	B	A
Comp. Ex. 1	Resin H3/Resin C2 (80/20)	A	D	B
Comp. Ex. 2	Resin H4/Resin C2 (80/20)	D	D	B
Comp. Ex. 3	Resin A2/Resin C2 (80/20)	A	D	B
Comp. Ex. 4	Resin A3/Resin C2 (80/20)	D	C	B
Comp. Ex. 5	Resin A4/Resin C2 (80/20)	B	D	C
Comp. Ex. 6	Resin A5/Resin C2 (80/20)	D	C	C

*Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that as compared to the toners of Comparative Examples 6-1 to 6-6, the toners of Examples 6-1 to 6-13 are excellent in all of low-temperature fixing ability, storage ability and triboelectric stability under high-temperature, high humidity conditions.

Example 7

Resins A to D

7.2 Production Example 2 of Resins

Resins E and F

A 5-liter four neck flask equipped with, a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple was charged with raw material monomers for a polyester other than trimellitic anhydride and an esterification catalyst as listed in Table 7-1. The mixture was subjected to a polycondensation reaction at 230° C. for 10 hours in a nitrogen atmosphere, and further subjected to a reaction at 230° C. and 8.0 kPa for 1 hour. Further, trimellitic anhydride shown in Table 7-1 was supplied thereto, and the mixture was subjected to a reaction at 210° C., and subjected to a reaction at 10 kPa until a desired softening point was

	TABLE 7-1

	Resin A	Resin B	Resin C	Resin D	Resin E	Resin F
	Amount	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	900	10	1800	20	—	—	—	—	—	—	—	—
1,2-Propanediol	760	10	—	—	—	—	—	—	—	—	—	—
Ethylene Glycol	—	—	—	—	744	12	744	12	—	—	—	—
Neopentyl Glycol	—	—	—	—	832	8	832	8	—	—	—	—
BPA-PO¹⁾	—	—	—	—	—	—	—	—	2450	7	2450	7
BPA-EO²⁾	—	—	—	—	—	—	—	—	975	3	975	3
Carboxylic Acid Component
Terephthalic Acid	2324	14	2324	14	2158	13	2158	13	1079	6.5	1079	6.5
Trimellitic Anhydride	576	3	576	3	768	4	768	4	384	2	384	2
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	22.8	—	23.5	—	22.5	—	22.5	—	24.4	—	24.4	—
Total Amount of Raw Material Monomers (g)	4560	4700	4502	4502	4888	4888
Amount of Alcohol A Contained in Alcohol	50	100	0	0	0	0
Component (% by mol)
Alcohol A/(Raw Material Monomers Other Than	24.6	62.1	0	0	0	0
Alcohol A) × 100 (parts by weight)
Softening Point (° C.)	137.3	100.8	138.2	123.1	138.9	98.6
Glass Transition Temperature (° C.)	67.9	60.4	62.3	57.5	67.8	60.2
Acid Value (mgKOH/g)	30.1	49.3	34.8	43.2	20.5	29.5

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

7.3 Examples 1 to 5 and Comparative Examples 1 to 6

One hundred parts by weight of a resin binder and a charge control resin as shown in Table 7-2, 4 parts by weight of a colorant “Regal 330R” (manufactured by Cabot Corporation), and 2 parts by weight of a polypropylene wax “NP-105” (manufactured by MITSUI CHEMICALS, INC., melting point: 140° C.) were mixed with a Henschel mixer. The mixture was melt-kneaded with a twin-screw extruder, and cooled, and the melt-kneaded product was then roughly pulverized with a hammer-mill to a size of 1 mm or so. The resulting roughly pulverized product was finely pulverized with an air jet-type pulverizer, and classified, to provide a toner particle having a volume-median particle size (D₅₀) of 7.5 μm.

7.4 Test Example 1

The same procedures as in Test Example 1 of Item 1.5 were carried out in both the test method and the evaluation criteria to evaluate low-temperature fixing ability.

The results are shown in Table 7-2.

7.5 Test Example 2

Triboelectric Chargeability

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 7-2.

7.6 Test Example 3

A toner was loaded to a printer “HL-2040” manufactured by Brother Industries Ltd., and an image having a print coverage of 5% was printed for 10,000 sheets continuously. During the course of printing, black solid images were printed for every 1,000 sheets, and the images obtained were observed visually, to evaluate solid image quality as triboelectric chargeability in accordance with the following evaluation criteria. The results are shown in Table 7-2. The larger the number of sheets until the lowering of optical density is caused, the more excellent the solid image quality.

8.1 Production Example 1 of Resins

A: The lowering in optical density did not take place up to printing 10,000 sheets.
B: The lowering in optical density was observed during printing between 5,000 sheets and 10,000 sheets.
C: The lowering in optical density was observed during printing between 3,000 sheets and 5,000 sheets.
D: The lowering in optical density was observed at less than 3,000 sheets.

	TABLE 7-2

	Charge	Evaluation of Toner
		Control	Low-Temp.	Storage	Triboelectric
No. 7-	Resin Binder¹⁾	Resin²⁾	Fixing Ability	Ability	Chargeability

Ex. 1	Resin A/Resin B (50/50)	CCR A = 7	A	A	A
Ex. 2	Resin A/Resin B (50/50)	CCR B = 7	A	A	B
Ex. 3	Resin A	CCR A = 7	B	A	A
Ex. 4	Resin A/Resin B (50/50)	CCR A = 25	B	B	B
Ex. 5	Resin A/Resin B (50/50)	CCR A = 5	A	A	B
Comp.	Resin A/Resin B (50/50)	—	A	A	C
Ex. 1
Comp.	Resin C/Resin D (50/50)	—	A	D	C
Ex. 2
Comp.	Resin C	—	A	D	C
Ex. 3
Comp.	Resin E/Resin F (50/50)	—	C	B	C
Ex. 4
Comp.	Resin C/Resin D (50/50)	CCR A = 7	A	D	C
Ex. 5
Comp.	Resin E/Resin F (50/50)	CCR A = 7	C	B	C
Ex. 6

¹⁾Inside the parenthesis shows a weight ratio of the resins.
²⁾The amount of a charge control resin used shows a weight ratio based on 100 parts by weight of resin binder.
CCR A: FCA-701PT (manufactured by FUJIKURAKASEI CO., LTD., quaternary ammonium salt group-containing styrene-acrylic copolymer, softening point: 123° C.)
CCR B: FCA-201PS (manufactured by FUJIKURAKASEI CO., LTD., quaternary ammonium salt group-containing styrene-acrylic copolymer, softening point: 111° C.)

It can be seen from the above results that as compared to the toners of Comparative Examples 7-1 to 7-6, the toners of Examples 7-1 to 7-5 are excellent in all of low-temperature fixing ability, storage ability, and triboelectric chargeability. Especially, it can be seen from the comparison of Comparative Examples 7-1 and 7-4 with Comparative Examples 7-3 and 7-5 that the toner containing a polyester in which an aliphatic polyhydric alcohol other than alcohol A is used or a polyester in which an aromatic polyhydric alcohol is used does not have improvement of triboelectric chargeability, even if a charge control resin is blended.

Example 8

Resins A to E

8.2 Production Example 2 of Resin

Resin F

	TABLE 8-1

	Resin A	Resin B	Resin C	Resin D	Resin E	Resin F
	Amount	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	900	10	900	10	900	10	1800	20	—	—	—	—
1,2-Propanediol	760	10	760	10	760	10	—	—	—	—	—	—
Ethylene Glycol	—	—	—	—	—	—	—	—	744	12	—	—
Neopentyl Glycol	—	—	—	—	—	—	—	—	832	8	—	—
BPA-PO¹⁾	—	—	—	—	—	—	—	—	—	—	2450	7
BPA-EO²⁾	—	—	—	—	—	—	—	—	—	—	975	3
Carboxylic Acid Component
Alkenylsuccinic Anhydride A	—	—	—	—	1072	4	—	—	—	—	—	—
Terephthalic Acid	2324	14	2324	14	1660	10	2324	14	2158	13	1079	6.5
Trimellitic Anhydride	576	3	576	3	576	3	576	3	768	4	384	2
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	22.8	—	22.8	—	24.8	—	23.5	—	22.5	—	24.4	—
Total Amount of Raw Material Monomers (g)	4560	4560	4968	4700	4502	4888
Amount of Alcohol A Contained in Alcohol	50	50	50	100	0	0
Component (% by mol)
Alcohol A/(Raw Material Monomers Other	24.6	24.6	22.1	62.1	0	0
Than Alcohol A) × 100 (parts by weight)
Softening Point (° C.)	137.3	100.8	138.2	118	123.1	120.3
Glass Transition Temperature (° C.)	67.9	61.2	62.3	73.1	60.2	61.0
Acid Value (mgKOH/g)	30.1	49.3	34.8	35.2	43.2	20.5

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

8.3 Examples 1 to 5 and Comparative Examples 1 to 4

One hundred parts by weight of a resin binder as shown in Table 8-2, 6 parts by weight of a magenta pigment “Super Magenta R” (manufactured by DIC Corporation, P.R. 122), 1 part by weight of a negatively chargeable charge control agent “BONTRON S-34” (manufactured by Orient Chemical Co., Ltd.), and 2 parts by weight of a paraffin wax “HNP-9” (manufactured by Nippon Seiro, melting point: 75° C.) were sufficiently mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with a unidirectional rotary twin-screw extruder at a roller rotational speed of 200 r/min and a heating temperature inside the roller of 80° C. The resulting melt-kneaded product was cooled and roughly pulverized, and thereafter pulverized with a jet mill, and a pulverized product was classified, to provide a toner particle having a volume-median particle size (D₅₀) of 8.0 μM.

To 100 parts by weight of the resulting toner particle was added 1.0 part by weight of each of external additives shown in Table 8-2, and the mixture was blended with a Henschel mixer for 3 minutes, to provide each of the toners.

8.4 Test Example 1

8.5 Test Example 2

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 8-2.

8.6 Test Example 3

Transferability

A toner was loaded in a color printer “MICROLINE 5400” (manufactured by Oki Data Corporation) and solid image was printed out. The amount of toner on the photoconductor of the solid image was adjusted to 0.40 to 0.50 mg/cm², and the machine was stopped in the course of printing of the solid image. A mending tape was adhered to a photoconductor which passed through a transfer member, so that a toner remaining on the photoconductor without being transferred was transferred to the mending tape, and the mending tape was removed from the photoconductor. The removed mending tape and an unused mending tape were determined with “CR-321” (manufactured by Minolta), and the transferability was evaluated on the basis of the difference in hues (ΔE) calculated from the following formula. The results are shown in Table 8-2.
ΔE=√{square root over ((L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²)}{square root over ((L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²)}{square root over ((L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²)} [Math 2]

wherein L₁*, a₁* and b₁* are each of the measurement values in the removed mending tape, and each of L₂*, a₂* and b₂* are each of the measurement values in the unused mending tape.

9.1 Production Example 1 of Resins

A: Difference in hues ΔE is less than 3.0.
B: Difference in hues ΔE is 3.0 or more and less than 4.0.
C: Difference in hues ΔE is 4.0 or more.

	TABLE 8-2

	Evaluation of Toner
			Low-Temp.
		External	Fixing	Storage
No. 8-	Resin Binder¹⁾	Additive²⁾	Ability	Ability	Transferability

Ex. 1	Resin A/Resin B (50/50)	External	A	A	A
		Additive A
Ex. 2	Resin A/Resin B (50/50)	External	A	A	B
		Additive B
Ex. 3	Resin A/Resin D (50/50)	External	A	A	A
		Additive A
Ex. 4	Resin C/Resin B (50/50)	External	A	B	B
		Additive A
Ex. 5	Resin D	External	B	A	A
		Additive A
Comp.	Resin E	External	A	D	C
Ex. 1		Additive A
Comp.	Resin F	External	C	B	C
Ex. 2		Additive A
Comp.	Resin A/Resin B(50/50)	External	A	A	C
Ex. 3		Additive C
Comp.	Resin A/Resin B(50/50)	External	A	A	C
Ex. 4		Additive D

¹⁾Inside the parenthesis shows a weight ratio of the resins.
²⁾External Additive A: Hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., average particle size 35 nm, hydrophobic treatment agent: HMDS) External Additive B: Hydrophobic silica “TG-C243” (manufactured by Cabot Corporation, average particle size 100 nm, hydrophobic treatment agent: OTES + HMDS) External Additive C: Hydrophobic silica “R-972” (manufactured by Nippon Aerosil Co., Ltd., average particle size 16 nm, hydrophobic treatment agent: DMDS) External Additive D: Hydrophobic silica “TSX-55” (manufactured by Shin-Etsu Chemical Co. Ltd., average particle size 300 nm, hydrophobic treatment agent: HMDS)

It can be seen from the above results that as compared to the toners of Examples 8-1 to 8-5, the toner of Comparative Example 8-1 containing a resin binder in which an aliphatic polyhydric alcohol other than the alcohol A is used is deficient in storage ability and transferability, even while having favorable low-temperature fixing ability, and that the toner of Comparative Example 8-2 containing a resin binder in which an aromatic polyhydric alcohol is used is insufficient in all the properties. Also, it can be seen that both of the toner of Comparative Example 8-3 in which an external additive having a too small average particle size is used and the toner of Comparative Example 8-4 in which an external additive having a too large average particle size is used have markedly lowered transferability.

Example 9

Resins A, B, and D to F

9.2 Production Example 2 of Resin

9.3 Production Example 3 of Resin

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractional distillation tube through which hot water at 100° C. was allowed to flow, a stirrer, and a thermocouple was charged with raw material monomers for a polyester other than fumaric acid and trimellitic anhydride, and an esterification catalyst as listed in Table 9-1. The mixture was kept at 180° C. for 1 hour in a nitrogen atmosphere, and heated from 180° to 230° C. at a rate of 10° C./hr, and the heated mixture was then subjected to a polycondensation reaction at 230° C. for 10 hours, and further subjected to a reaction under a reduced pressure at 230° C. and 40 kPa for 1 hour. After cooling the reaction mixture to 180° C., fumaric acid, trimellitic anhydride, and tert-butyl catechol shown in Table 9-1 were supplied thereto. The mixture was heated to 210° C. over 4 hours, and the heated mixture was subjected to a reaction at 210° C. and normal pressure for 2 hours, and subjected to a reaction at 210° C. and 10 kPa until a desired softening point was reached, to provide a polyester.

Resin G

	TABLE 9-1

	Resin A	Resin B	Resin C	Resin D	Resin E	Resin F	Resin G
	Amount	Amount	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	900	10	900	10	900	10	1800	20	900	10	—	—	—	—
1,2-Propanediol	760	10	760	10	760	10	—	—	760	10	—	—	—	—
Ethylene Glycol	—	—	—	—	—	—	—	—	—	—	620	10	—	—
Neopentyl Glycol	—	—	—	—	—	—	—	—	—	—	1040	10	—	—
BPA-PO¹⁾	—	—	—	—	—	—	—	—	—	—	—	—	2450	7
BPA-EO²⁾	—	—	—	—	—	—	—	—	—	—	—	—	975	3
Carboxylic Acid Component
Fumaric Acid	—	—	—	—	464	4	—	—	—	—	—	—	—	—
Alkenylsuccinic Anhydride A	—	—	1072	4	—	—	—	—	—	—	—	—	—	—
Terephthalic Acid	2656	16	1992	12	1992	12	2656	16	2324	14	2158	13	996	6
Trimellitic Anhydride	384	2	384	2	384	2	384	2	576	3	768	4	384	2
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	23.5	—	25.5	—	22.5	—	24.2	—	—	—	22.9	—	24.0	—
Titanium Compound³⁾	—	—	—	—	—	—	—	—	22.8	—	—	—	—	—
Polymerization Inhibitor
tert-Butyl Catechol	—	—	—	—	2.7	—	—	—	—	—	—	—	—	—
Total Amount of Raw Material	4700	5108	4500	4840	4560	4586	4805
Monomers (g)
Amount of Alcohol A Contained	50	50	50	100	50	0	0
in Alcohol Component
(% by mol)
Alcohol A/(Raw Material	23.7	21.4	25.0	59.2	24.6	0	0
Monomers Other Than Alcohol
A) × 100 (parts by weight)
Softening Point (° C.)	130.2	126.7	125.3	127.7	101.2	123.1	125.4
Glass Transition Temperature	65.4	59.4	63.6	72.6	59.6	60.2	63.4
(° C.)
Acid Value (mgKOH/g)	35.7	26.4	30.1	40.2	41.2	43.2	25.6

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
³⁾Titanium Diisopropylate bis(Triethanolamininate)

9.4 Examples 1 to 13 and Comparative Examples 1 to 4

One hundred parts by weight of a resin binder as shown in Table 9-2, 6 parts by weight of a cyan pigment “Toner Cyan BG” (manufactured by Clariant GmbH, C.I. Pigment Blue 15:3), a charge control agent as shown in Table 9-2, and 2 parts by weight of a paraffin wax “HNP-9” (manufactured by Nippon Seiro, melting point: 75° C.) were sufficiently mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with a unidirectional rotary twin-screw extruder at a roller rotational speed of 200 r/min and a heating temperature inside the roller of 80° C. The resulting melt-kneaded product was cooled and roughly pulverized, and thereafter pulverized with a jet mill, and a pulverized product was classified, to provide a toner particle having a volume-median particle size (D₅₀) as shown in Table 9-2.

9.5 Test Example 1

9.6 Test Example 2

Initial Rise in Triboelectric Chargeability

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 9-2.

9.7 Test Example 3

A 50 ml polyethylene bottle was charged with 0.6 g of a toner and 19.4 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo, average particle size: 90 and the components were mixed with a ball-mill at a rate of 250 r/min, and triboelectric charges of the toners at the time of 1 minute and 10 minutes were determined with a q/m meter (manufactured by EPPING). After a given period of mixing time, a developer in defined amounts was supplied into a cell provided in the q/m meter, and only the toner was aspirated for 90 seconds through a sieve having a sieve opening of 32 μm (made of stainless steel, twilled, wire diameter: 0.0035 mm). The voltage change generated on the carrier at this time was monitored and initial rise in triboelectric chargeability was evaluated in accordance with the following evaluation criteria. The results are shown in Table 9-2.

10.1 Production Examples 1 to 6 of Resins

A value for (triboelectric charges at a mixing time of 1 minute)/(triboelectric charges at a mixing time of 10 minutes) is:

A: 0.95 or more
B: 0.9 or more and less than 0.95
C: less than 0.9

	TABLE 9-2

	Evaluation of Toner
		Charge		Low-Temp.		Initial Rise in
		Control	D₅₀	Fixing	Storage	Triboelectric
No. 9-	Resin Binder¹⁾	Agent²⁾	(μm)	Ability	Ability	Chargeability

Ex. 1	Resin A/Resin E(50/50)	C-1(1.5)	7.0	A	A	A
Ex. 2	Resin A/Resin E(50/50)	C-2(1.5)	7.2	A	A	A
Ex. 3	Resin A/Resin E(50/50)	C-3(1.5)	7.1	A	A	A
Ex. 4	Resin A/Resin E(50/50)	C-4(1.5)	6.8	A	A	A
Ex. 5	Resin A/Resin E(50/50)	C-1(0.5)	6.9	A	A	B
Ex. 6	Resin A/Resin E(50/50)	C-1(3.0)	7.0	A	A	B
Ex. 7	Resin B/Resin E(50/50)	C-1(1.5)	7.0	A	B	A
Ex. 8	Resin C/Resin E(50/50)	C-1(1.5)	7.3	A	B	A
Ex. 9	Resin D/Resin E(50/50)	C-1(1.5)	7.4	B	A	A
Ex. 10	Resin A	C-1(1.5)	7.1	A	A	A
Ex. 11	Resin E	C-1(1.5)	7.1	A	B	A
Ex. 12	Resin F/Resin E(50/50)	C-1(1.5)	7.0	A	B	B
Ex. 13	Resin G/Resin E(50/50)	C-1(1.5)	6.9	B	B	B
Comp.	Resin F	C-1(1.5)	7.0	A	D	C
Ex. 1
Comp.	Resin G	C-1(1.5)	7.2	C	B	C
Ex. 2
Comp.	Resin A/Resin E(50/50)	C-5(1.5)	7.1	A	A	C
Ex. 3
Comp.	Resin G	C-5(1.5)	7.2	C	B	B
Ex. 4

¹⁾Inside the parenthesis shows a weight ratio of the resins.
²⁾Inside the parenthesis shows an amount of a charge control agent used based on 100 parts by weight of the resin binder.
C-1: Chromium complex of a salicylic acid compound “BONTRON E-81” (manufactured by Orient Chemical Co., Ltd.)
C-2: Zinc complex of salicylic acid compound “BONTRON E-84” (manufactured by Orient Chemical Co., Ltd.)
C-3: Boron complex of a benzylic acid compound “LR-147” (manufactured by Nippon Carlit, Ltd.)
C-4: Aluminum complex of a benzylic acid compound “LR-297” (manufactured by Nippon Carlit, Ltd.)
C-5: Metal azo complex “T-77” (manufactured by Hodogaya Chemical Co., Ltd.)

It can be seen from the above results that as compared to the toners of Examples 9-1 to 9-13, the toner of Comparative Example 9-1 containing a resin binder in which an aliphatic polyhydric alcohol other than an alcohol A is used is deficient in storage ability and initial rise in triboelectric chargeability, even while having a favorable low-temperature fixing ability, and that the toner of Comparative Example 9-2 containing a resin binder in which an aromatic polyhydric alcohol is used is insufficient in all the properties. Also, it can be seen that the toner of Comparative Example 9-3 containing a charge control agent comprising a metal azo complex has a markedly lowered initial rise of triboelectric chargeability. It can be seen from the comparison of Comparative Example 9-2 and Comparative Example 9-4 that the toner containing a resin binder in which an alcohol A is not used has improved initial rise in triboelectric chargeability by a metal azo complex.

Example 10

10.2 Production Example 7 of Resin

A 5-liter four neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with an alcohol component, a carboxylic acid component other than fumaric acid and trimellitic anhydride, and an esterification catalyst as listed in Table 10-1. The mixture was subjected to a reaction at 230° C. for 8 hours in a nitrogen atmosphere, and then cooled to 180° C., and fumaric acid was then supplied thereto. The mixture was kept at 180° C. for 1 hour, and heated from 180° to 210° C. at a rate of 10° C./hr, and the heated mixture was then subjected to a polycondensation reaction at 210° C. for 2 hours, and further subjected to a reaction at 210° C. and 8.0 kPa for 1 hour. After cooling the reaction mixture to 205° C., trimellitic anhydride shown in Table 10-1 was supplied thereto, and the mixture was subjected to a reaction at 205° C. for 1 hour, and subjected to a reaction at 205° C. and 10 kPa until a desired softening point was reached, to provide a polyester (Resin G).

	TABLE 10-1

	Resin A	Resin B	Resin C	Resin D	Resin E	Resin F	Resin G


Alcohol Component
2,3-Butanediol (Alcohol A)	848.7 g	993.6 g	449.7 g	533.6 g	1685.5 g	—	—
1,2-Propanediol	514.0 g	268.1 g	569.7 g	837.1 g	—	—	—
Neopentyl Glycol	—	—	259.5 g	—	—	855.6 g	—
Ethylene Glycol	132.2 g	—	103.1 g	—	—	530.9 g	—
BPA-PO¹⁾	—	—	—	—	—	—	3174.8 g
Carboxylic Acid Component
Terephthalic Acid	2808.2 g	1830.6 g	1795.1 g	1966.4 g	1552.7 g	2620 g	—
Isophthalic Acid	—	844.9 g	414.3 g	—	—	—	—
Trimellitic Anhydride	102.4 g	162.9 g	159.7 g	426.8 g	718.4 g	193.4 g	142.4 g
Purified Rosin	—	—	—	842.7 g	—	—	—
Itaconic Acid	—	—	—	220.2 g	243.4 g	—	—
Fumaric Acid	—	—	—	—	—	—	391.6 g
Esterification Catalyst
Tin 2-Ethylhexanoate	12.6 g	16.8 g	—	—	—	—	—
Dibutyltin Oxide	—	—	8.4 g	—	8.4 g	8.4 g	8.4 g
tetra-n-Butyl Titanate	—	—	—	25.2 g	—	—	—
Amount of Alcohol A Contained in Alcohol	51.5	75.8	30.0	35.0	100	0	0
Component (% by mol)
Alcohol A/(Raw Material Monomers Other	23.8	32.0	13.6	12.4	67.0	0	0
Than Alcohol A) × 100 (parts by weight)
Glass Transition Temperature (° C.)	68.6	60.6	64.6	58.2	73.6	53.1	63.6
Acid Value (mgKOH/g)	21.5	25.2	15.3	28.2	79.5	7.8	19.2
Hydroxyl Value (mgKOH/g)	23.8	30.3	33.2	39.9	56.1	49.2	32.8

¹⁾Polyoxypropylene(2.0)-2,2-bis(4-hydroxyphenyl)propane

10.3 Example 1

A 5-liter stainless steel vessel was charged with 100 g of Resin A, 100 g of Resin B and 100 g of nonionic surfactant (polyoxyethylene lauryl ether (EO=9 mol added), cloud point: 98° C., HLB: 15.3), and the mixture was melted at 170° C., while stirring with a paddle-shaped stirrer at a rate of 200 r/min. The contents were stabilized at 95° C., a temperature lower than cloud point of the nonionic surfactant by 3° C., and 75.5 g of an aqueous sodium hydroxide solution (concentration: 5% by weight) was added dropwise to the mixture as a neutralizing agent while stirring with a paddle-shaped stirrer at a rate of 200 r/min. Subsequently, deionized water was added dropwise thereto at a rate of 6 g/min while stirring with a paddle-shaped stirrer at a rate of 300 r/m, totaling in an amount of 1624.5 g of deionized water. During this time, the temperature of the system was kept at 95° C. The mixture was passed through a 200-mesh wire gauze (opening: 105 μm), to provide a resin dispersion containing fine resin particles. The resin particles (primary particles) in the resulting resin dispersion had a volume-median particle size (D₅₀) of 0.45 μm and a solid content of 12.0% by weight, and no resin components remaining on the wire gauze.

Four hundred grams of the resulting resin dispersion (concentration: 12.3% by weight), 40 g of an aqueous dispersion of a cyan pigment (concentration: 5% by weight), and 7 g of an aqueous dispersion of a paraffin wax (HNP-9, manufactured by Nippon Seiro, melting point: 78° C.) (concentration: 35% by weight, nonionic surfactant: 5% by weight of EMULGEN 108 (manufactured by KAO Corporation), dispersion diameter of the wax (volume-median particle size: 0.30 μm) were mixed in a 1-liter vessel at room temperature.

Next, an aqueous solution of a 1 g portion of calcium chloride was added to this mixture as an aggregating agent, and the pH of the dispersion was adjusted to 7 with an aqueous sodium carbonate solution (concentration: 10% by weight). Thereafter, the dispersion was stirred with a homo-mixer at a rotational speed of 5,000 r/min at room temperature for 1 hour. As a consequence, the resulting mixed dispersion was transferred to a 1-liter autoclave, heated to 90° C., and stirred at 500 r/min for 6 hours, to form aggregated particles.

Thereafter, the dispersion was heated to 100° C., and stirred for an additional 1 hour, to unify the aggregated particles, and thereafter the steps of aspiration, filtering, washing and drying were carried out to provide a colored powder of fine resin particles. The colored powder of fine resin particles had a volume-median particle size of 6.8 μm and a water content of 0.3% by weight.

To 100 parts by weight of the resulting colored powder of fine resin particles was added 1.0 part by weight of a hydrophobic silica (TS530, manufactured by Wacker Chemicals, number-average particle size: 8 nm). The mixture was mixed with a Henschel mixer, and subjected to an external addition treatment to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.8 μm.

10.4 Example 2

Fifty parts by weight of Resin C, 50 parts by weights of Resin D, 4.0 parts by weight of a yellow colorant (Paliotol D1155, manufactured by BASF), 2.5 parts by weight of a charge control agent (BONTRON E-84, manufactured by Hodogaya Chemical Co., Ltd.), and 4 parts by weight of a paraffin wax (HNP-9, manufactured by Nippon Seiro, melting point: 78° C.) were previously mixed with a Henschel mixer, and thereafter the mixture was melt-kneaded with an open roller-type kneader, cooled and pulverized, to provide 1 mm chips of the kneaded product.

A 5-liter stainless steel vessel was charged with 200 g of resulting kneaded product and 100 g of a nonionic surfactant (polyoxyethylene lauryl ether (EO=9 mol added), cloud point: 98° C., HLB: 15.3), and the mixture was melted at 170° C. while stirring with a paddle-shaped stirrer at rate of 200 r/min. The content was stabilized at 95° C., a temperature lower than cloud point of the nonionic surfactant by 3° C., and 75.5 g of an aqueous sodium hydroxide solution (concentration: 5% by weight) was added dropwise to the mixture as a neutralizing agent while stirring with a paddle-shaped stirrer at a rate of 200 r/min. Subsequently, deionized water was added dropwise thereto at a rate of 6 g/min while stirring with a paddle-shaped stirrer at a rate of 300 r/m, totaling in an amount of 1624.5 g of deionized water. During this time, the temperature of the system was kept at 95° C., and the mixture was passed through a 200-mesh wire gauze (opening: 105 μm), to provide a resin dispersion containing fine resin particles. The resin particles (primary particles) in the resulting resin dispersion had a volume-median particle size (D₅₀) of 0.45 μm and a solid content of 12.0% by weight, and no resin components remaining on the wire gauze.

Next, an aqueous solution of a 1 g portion of calcium chloride was added to this mixture as an aggregating agent, and the pH of the solution was adjusted to 7 with an aqueous sodium carbonate solution (concentration: 10% by weight). Thereafter, the mixture solution was stirred with a homo-mixer at a rotational speed of 5,000 r/min at room temperature for 1 hour. The generated mixed dispersion was transferred to a 1-liter autoclave, heated to 105° C., and stirred at 500 r/min for 6 hours, to form aggregated particles.

Thereafter, the dispersion was heated to 125° C., and stirred for an additional 1 hour, to unify the aggregated particles, and thereafter the steps of aspiration, filtering, washing and drying were carried out to provide colored powder of fine resin particles. The colored powder of fine resin particles had a volume-median particle size (D₅₀) of 6.7 μm and a water content of 0.3% by weight.

To 100 parts by weight of the resulting colored powder of fine resin particles was added 1.0 part by weight of a hydrophobic silica (TS530, manufactured by Wacker Chemicals, number-average particle size: 8 nm). The mixture was mixed with a Henschel mixer and subjected to an external addition treatment, to provide a yellow toner. The resulting yellow toner had a volume-median particle size (D₅₀) of 6.8 μm.

10.5 Example 3

A 5-L vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube was charged with 600 g of methyl ethyl ketone, and then 200 g of Resin E was added thereto at room temperature to dissolve. Ten grams of triethylamine was added to the resulting solution to neutralize the solution, and subsequently 2,000 g of ion-exchanged water was added thereto. Thereafter, methyl ethyl ketone was distilled off at a stirring rate of 250 r/min at a temperature of 50° C. or less under a reduced pressure, to provide a self-dispersible aqueous dispersion of resin particles (resin content: 9.6% by weight (on a solid basis)). Polyester particles dispersed in the resulting resin dispersion had a weight-average particle size of 0.3 μm.

Fifty grams of copper phthalocyanine (manufactured by DAINICHISEIKA COLOR & CHEMICALS MFG. CO.), 5 g of a nonionic surfactant (EMULGEN 150, manufactured by KAO Corporation) and 200 g of ion-exchanged water were mixed, and the copper phthalocyanine was dissolved. The mixture was dispersed for 10 minutes with a homogenizer to provide a colorant-dispersed dispersion.

A mixture of 50 g of a paraffin wax (HNP0190, manufactured by Nippon Seiro, melting point: 85° C.), 5 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) and 200 g of ion-exchanged water was heated to 95° C., and the paraffin wax was dispersed with a homogenizer. Thereafter, the mixture was subjected a dispersion treatment with a pressure jetting homogenizer, to provide a wax dispersion in which the paraffin wax was dispersed in an average particle size of 550 nm.

Fifty grams of a charge control agent (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.), 5 g of a nonionic surfactant (EMULGEN 150, manufactured by KAO Corporation) and 200 g of ion-exchanged water were mixed, the mixture was dispersed for 10 minutes using glass beads with a sand grinder, to prepare a charge control agent dispersion in which the charge control agent was dispersed in an average particle size of 500 nm. However, remnants of coarse particles in the dispersion were observed.

Four-hundred and ninety grams of the resulting resin particle dispersion, 20 g of a colorant dispersion, 15 g of a wax dispersion, 7 g of a charge control agent dispersion and 2 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) were mixed in a round-shaped stainless steel flask with a homogenizer. The mixture was dispersed, and thereafter heated to 48° C., while stirring the contents inside the flask in a heating oil bath. Further, after the dispersion was kept at 48° C. for 1 hour, it was confirmed that aggregated particles having a weight-average particle size of 7.0 μm were formed.

Three grams of an anionic surfactant (PELEX SS-L, manufactured by KAO Corporation) was added to the aggregated particle dispersion in which the aggregated particles were formed. Thereafter, the above-mentioned stainless steel flask was equipped with a reflux tube, and the dispersion was heated to 80° C. at a rate of 5° C./min while continuously stirring, and kept thereat for 5 hours, to unify and fuse the aggregated particles. Thereafter, the unified particles were cooled, filtered, and sufficiently washed with ion-exchanged water and dried, to provide colored powder of fine resin particles. The resulting colored powder of fine resin particles had a volume-median particle size (D₅₀) of 7.1 μm.

To 100 parts by weight of the resulting colored powder of fine resin particles was added 1.0 part by weight of a hydrophobic silica (TS530, manufactured by Wacker Chemicals, number-average particle size: 8 nm). The mixture was mixed with a Henschel mixer and subjected to an external addition treatment to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 7.1 μm.

10.6 Example 4

The same procedures as in Example 1 were carried out except that 50 parts by weight of Resin A and 50 parts by weight of Resin F were used in place of Resin A to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.7 μm.

10.7 Comparative Example 1

The same procedures as in Example 1 were carried out except that 100 parts by weight of Resin G were used in place of Resin A to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.8 μm.

10.8 Comparative Example 2

The same procedures as in Example 1 were carried out except that 100 parts by weight of Resin F were used in place of Resin A to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.7 μm.

10.9 Test Example 1

Hydrolytic Resistance

A 100-ml eggplant-shaped flask was charged with 1.0 g of a resin binder used in each of Examples and Comparative Examples shown in Table 10-2, 20 ml of a 0.1 mol/L methanol solution of potassium hydroxide was added thereto, and further 20 ml of distilled water was added thereto. The contents were heated in a water bath at 90° C. for 5 hours. After the termination of heating for 5 hours, the solution was neutralized with 0.1 mol/L of hydrochloric acid, and the solvent was then removed therefrom, and a residual resin was dried. A glass transition temperature (Tg) of the resulting resin was determined, and the Tg's before and after the test were compared to evaluate hydrolytic resistance in accordance with the following evaluation criteria.

A: A temperature difference in Tg's before and after the test is less than 1° C.
B: A temperature difference in Tg's before and after the test is 1° C. or more and less than 3° C.
C: A temperature difference in Tg's before and after the test is 3° C. or more and less than 6° C.
D: A temperature difference in Tg's before and after the test is 6° C. or more.

10.10 Test Example 2

A: The lowest fixing temperature is less than 140° C.
B: The lowest fixing temperature is 140° C. or more and less than 160° C.
C: The lowest fixing temperature is 160° C. or more.

10.11 Test Example 3

Hot Offset Resistance

In Test Example 2, a temperature at which offset is initially confirmed is visually judged, upon sequentially raising a temperature of a fixing roller from 90° to 240° C., and hot offset resistance was evaluated in accordance with the following evaluation criteria. The results are shown in Table 10-2.

[Evaluation Criteria]

A: The hot offset generation temperature is 220° C. or more.
B: The hot offset generation temperature is 200° C. or more and less than 220° C.
C: The hot offset generation temperature is 180° C. or more and less than 200° C.
D: The hot offset generation temperature is less than 180° C.

10.12 Test Example 4

11.1 Production Example 1 of Resins

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 10-2.

	TABLE 10-2

	Evaluation of Toner
			Low-
			Temp.
	Resin Binder	Hydrolytic	Fixing	Hot Offset	Storage
No. 10-	(parts by weight)	Resistance	Ability	Resistance	Ability

Ex. 1	Resin A/Resin	A	A	A	A
	B (50/50)
Ex. 2	Resin C/Resin	B	A	B	B
	D (50/50)
Ex. 3	Resin E	A	B	A	A
Ex. 4	Resin A/Resin	B	A	B	B
	F (50/50)
Comp.	Resin G	C	C	B	A
Ex. 1
Comp.	Resin F	D	A	C	D
Ex. 2

* Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that as compared to the toners of Comparative Examples 10-1 and 10-2, the toners of Examples 10-1 to 10-4 containing a polyester in which an aliphatic polyhydric alcohol having two or more secondary carbon atoms with a hydroxyl group bound thereto is used in a proper amount have favorable storage ability and low-temperature fixing ability.

Example 11

Resins A, B, D to H, and J

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers other than trimellitic anhydride and an esterification catalyst, as listed in Table 11-1 or 11-2. The mixture was heated in a mantle heater to 180° C. in a nitrogen atmosphere, and thereafter heated to 230° C. over 10 hours. Thereafter, having confirmed that a conversion rate at 230° C. reached 95% or higher, the reaction mixture was cooled to 210° C. Trimellitic anhydride shown in Table 11-1 or 11-2 was supplied thereto, and the mixture was subjected to a reaction at a normal pressure for 1 hour, and then subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a polyester. Here, the conversion rate refers to a value calculated by: [amount of water generated in reaction/theoretical amount of generated water]×100.

11.2 Production Example 2 of Resin

11.3 Production Example 3 of Resin

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers other than fumaric acid and trimellitic anhydride and an esterification catalyst, as listed in Table 11-1. The mixture was heated in a mantle heater to 180° C. in a nitrogen atmosphere, and thereafter heated to 230° C. over 10 hours. Thereafter, having confirmed that a conversion rate at 230° C. reached 95% or higher, the reaction mixture was cooled to 180° C. Trimellitic anhydride, fumaric acid and tert-butyl catechol listed in Table 11-1 were supplied thereto, and the mixture was heated to 210° C. over 3 hours, and then subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a polyester.

Resin I

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers other than trimellitic anhydride and an esterification catalyst, as listed in Table 11-2. The mixture was heated in a mantle heater to 235° C. in a nitrogen atmosphere, and thereafter subjected to a reaction at 235° C. for 10 hours. Thereafter, the mixture was subjected to a reaction at 235° C. and 8 kPa for 1 hour, and cooled to 210° C. Trimellitic anhydride shown in Table 11-2 was supplied thereto, and the mixture was subjected to a reaction at normal pressure for 1 hour, and subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a polyester.

	TABLE 11-1

	Resin A	Resin B	Resin C	Resin D	Resin E
	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	900	10	1800	20	900	10	—	—	900	10
1,2-Propanediol	761	10	—	—	761	10	1218	16	761	10
1,3-Propanediol	—	—	—	—	—	—	—	—	—	—
2,4-Hexanediol	—	—	—	—	—	—	472	1.3	—	—
Carboxylic Acid Component
Alkenylsuccinic Anhydride A (ASAN)	1340	5	1340	5	1340	5.0	1072	4	268	1
Fumaric Acid	—	—	—	—	348	1.3	—	—	—	—
Terephthalic Acid	2158	13	2158	13	1660	10	1992	12	2490	15
Trimellitic Anhydride	384	2	384	2	384	2	576	3	384	2
Esterification Catalyst
Dibutyltin Oxide	—	—	—	—	—	—	—	—	25.0	—
Tin(II) 2-Ethylhexanoate	27.7	—	28.4	—	27.0	—	—	—	—	—
Titanium Compound¹⁾	—	—	—	—	—	—	26.6	—	—	—
Polymerization Initiator
tert-Butyl Catechol	—	—	—	—	2.7	—	—	—	—	—
Total Amount of Raw Material Monomers (g)	5543	5682	5393	5330	4803
Amount of Alcohol A Contained in Alcohol	50	100	50	7.5	50
Component (% by mol)
Amount of ASAN Contained in Carboxylic	25.0	25.0	29.4	21.1	5.6
Acid Component (% by mol)
Alcohol A/(Raw Material Monomers Other	19.4	46.4	20	9.7	23.1
Than Alcohol A) × 100 (parts by weight)
Softening Point (° C.)	112.3	117.4	101.1	114.2	110.6
Glass Transition Temperature (° C.)	58.7	59.7	52.1	59.1	62.4
Acid Value (mgKOH/g)	25.3	31.4	25.1	18.4	22.4

¹⁾Titanium Diisopropylate bis(Triethanolaminate)

	TABLE 11-2

	Resin F	Resin G	Resin H	Resin I	Resin J
	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers
Alcohol Component
2,3-Butanediol	900	10	720	8	—	—	—	—	—	—
1,2-Propanediol	761	10	457	6	—	—	—	—	—	—
Ethylene Glycol	—	—	372	6	620	10	—	—	620	10
Neopentyl Glycol	—	—	—	—	1040	10	—	—	1040	10
BPA-PO¹⁾	—	—	—	—	—	—	1750	5	—	—
BPA-EO²⁾	—	—	—	—	—	—	1625	5	—	—
Carboxylic Acid Component
Alkenylsuccinic Anhydride A (ASAN)	2144	8	1340	5	1340	5	—	—	—	—
Terephthalic Acid	1328	8	2158	13	2158	13	1162	7	2490	15
Trimellitic Anhydride	576	3	384	2	384	2	288	1.5	768	4
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	28.5	—	27.2	—	27.7	—	24.1	—	24.6	—
Total Amount of Raw Material Monomers (g)	5709	5431	5542	4825	4918
Amount of Alcohol A Contained in Alcohol	50	40	0	0	0
Component (% by mol)
Amount of ASAN Contained in Carboxylic Acid	42.1	25.0	25.0	0	0
Component (% by mol)
Alcohol A/(Raw Material Monomers Other Than	18.7	15.3	0	0	0
Alcohol A) × 100 (parts by weight)
Softening Point (° C.)	114.5	110.6	105.4	118.9	108.6
Glass Transition Temperature (° C.)	50.6	52.1	47.7	56.3	50.1
Acid Value (mgKOH/g)	18.4	26.3	36.5	19.8	38.5

¹⁾Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2,2)-2,2-bis(4-hydroxyphenyl)propane

11.4 Examples 1 to 12 and Comparative Examples 1 to 3

[Preparation of Resin Dispersion]

To a 5-L vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, 600 g of methyl ethyl ketone was supplied, and 200 g of a resin binder, as listed in Table 11-3, was added thereto at room temperature to dissolve. Ten grams of triethylamine was added to the resulting solution to neutralize the solution, and subsequently 2,000 g of ion-exchanged water was added thereto. Thereafter, the methyl ethyl ketone was distilled off from the mixture at a stirring rate of 250 r/min at a temperature of 50° C. or less under a reduced pressure, to provide a self-dispersible aqueous dispersion of resin particles (resin content: 9.6% by weight (on a solid basis)). Polyester particles (primary particles) dispersed in the resulting resin dispersion had an average particle size of 0.3 μm.

Fifty grams of copper phthalocyanine (manufactured by DAINICHISEIKA COLOR & CHEMICALS MFG. CO.), 5 g of nonionic surfactant (EMULGEN 150, manufactured by KAO Corporation, polyoxyethylene lauryl ether, HLB: 18.4, cloud point: 100° C. or more) and 200 g of ion-exchanged water were mixed, and copper phthalocyanine was dissolved. The mixture was dispersed for 10 minutes with a homogenizer to provide a dispersed colorant dispersion.

A mixture of 50 g of a paraffin wax (HNP0190, manufactured by Nippon Seiro, melting point: 85° C.), 5 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) and 200 g of ion-exchanged water was heated to 95° C., and the paraffin wax was dispersed with a homogenizer. Thereafter, the mixture was subjected to a dispersion treatment with a pressure jetting homogenizer, to provide a releasing agent dispersion in which the paraffin wax was dispersed in an average particle size of 550 nm.

Fifty grams of a charge control agent (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.), 5 g of a nonionic surfactant (EMULGEN 150, manufactured by KAO Corporation, polyoxyethylene lauryl ether, HLB: 18.4, cloud point: 100° C. or more) and 200 g of ion-exchanged water were mixed, and the mixture was dispersed for 10 minutes using glass beads with a sand grinder, to prepare a charge control agent dispersion in which the charge control agent was dispersed in an average particle size of 500 nm. However, remnants of coarse particles in the dispersion were observed.

Four-hundred and ninety grams of a resin particle dispersion, 20 g of colorant dispersion, 15 g of a releasing agent dispersion, 7 g of a charge control agent dispersion and 2 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) obtained were mixed in a round-shaped stainless steel flask with a homogenizer to disperse. Thereafter, the dispersion was heated to 48° C., while stirring the contents inside the flask in a heating oil bath. Further, after the dispersion was kept at 48° C. for 1 hour, it was confirmed that aggregated particles having a weight-average particle size of 6.0 μm were formed.

Three grams of an anionic surfactant (PELEX SS-L, manufactured by KAO Corporation) was added to the aggregated particle dispersion in which the aggregated particles were formed, and thereafter the above-mentioned stainless steel flask was equipped with a reflux tube. The dispersion was heated to 80° C. at a rate of 5° C./min while continuously stirring, and kept thereat for 5 hours, to unify and fuse the aggregated particles. Thereafter, the unified particles were cooled, filtered, and sufficiently washed with ion-exchanged water and dried, to provide colored powder of fine resin particles. The resulting colored powder of fine resin particles had a volume-median particle size (D₅₀) of 6.3 p.m.

Preparation of Resin Dispersion

To 100 parts by weight of the resulting colored powder of fine resin particles was added 1.0 part by weight of hydrophobic silica (TS530, manufactured by Wacker Chemicals, number-average particle size: 8 nm), and the mixture was mixed with a Henschel mixer and subjected to an external addition treatment, to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.5 μm.

11.5 Example 13

One thousand and three-hundred grams of Resin A, 100 g of an anionic surfactant (NEOPELEX G-15, manufactured by KAO Corporation, sodium dodecylbenzenesulfonate (solid content 15% by weight)), 100 g of a nonionic surfactant (EMULGEN 430, manufactured by KAO Corporation, polyoxyethylene oleyl ether (EO=26 mol added), HLB: 16.2, cloud point: 100° C. or more) and 689 g of a 5% by weight aqueous potassium hydroxide solution were dispersed in a 5-liter stainless steel vessel at 25° C., while stirring with a paddle-shaped stirrer at rate of 200 r/min. The contents were stabilized at 95° C., and kept thereat for 2 hours while stirring with a paddle-shaped stirrer at a rate of 200 r/min. Subsequently, deionized water was added dropwise thereto at a rate of 15 g/min, while stirring with a paddle-shaped stirrer at a rate of 200 r/m, totaling in an amount of 2845 g of deionized water. During this dropwise addition, the temperature of the system was kept at 95° C. After the system was cooled, the mixture was passed through a 150-mesh wire gauze (opening: 105 μm), to provide a resin dispersion containing fine resin particles. The resin particles (primary particles) in the resulting resin dispersion had an average particle size of 0.15 μm and a solid content of 31% by weight, and no resin components remained on the wire gauze.

Fifty grams of copper phthalocyanine (manufactured by DAINICHISEIKA COLOR & CHEMICALS MFG. CO.), 5 g of a nonionic surfactant (EMULGEN 150, manufactured by KAO Corporation, polyoxyethylene lauryl ether, HLB: 18.4, cloud point: 100° C. or more) and 200 g of ion-exchanged water were mixed, and copper phthalocyanine was dissolved. The mixture was dispersed for 10 minutes with a homogenizer, to provide a colorant-dispersed dispersion.

A mixture of 50 g of a paraffin wax (HNP0190, manufactured by Nippon Seiro, melting point: 85° C.), 5 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) and 200 g of ion-exchanged water was heated to 95° C., and the paraffin wax was dispersed with a homogenizer. Thereafter, the mixture was subjected to a dispersion treatment with a pressure jetting homogenizer, to provide a releasing agent dispersion in which the paraffin wax was dispersed in an average particle size of 550 nm.

Four-hundred and ninety grams of a resin particle dispersion, 20 g of colorant dispersion, 15 g of a releasing agent dispersion, 7 g of charge control agent dispersion and 2 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) obtained were mixed in a round-shaped stainless steel flask with a homogenizer (pH=7) to disperse. Thereafter, the mixture was heated to 48° C., while stirring the contents inside the flask in a heating oil bath. Further, after the dispersion was kept at 48° C. for 1 hour, it was confirmed that aggregated particles having a weight-average particle size of 6.0 μm were formed.

Three grams of an anionic surfactant (PELEX SS-L, manufactured by KAO Corporation) was added to the aggregated particle dispersion in which the aggregated particles were formed, and thereafter the above-mentioned stainless steel flask was equipped with a reflux tube. The dispersion was heated to 80° C. at a rate of 5° C./min while continuously stirring, and kept for 5 hours, to unify and fuse the aggregated particles. Thereafter, the unified particles were cooled, filtered, and sufficiently washed with ion-exchanged water and dried, to provide colored powder of fine resin particles. The resulting colored powder of fine resin particles had a volume-median particle size (D₅₀) of 6.3 μm.

To 100 parts by weight of the resulting colored powder of fine resin particles was added 1.0 part by weight of a hydrophobic silica (TS530, manufactured by Wacker Chemicals, number-average particle size: 8 nm), and the mixture was mixed with a Henschel mixer and subjected to an external addition treatment, to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.9 μm.

11.6 Test Example 1

Hydrolytic Resistance

The same procedures as in Test Example 1 of Item 10.9 were carried out using a resin binder used in each of Examples and Comparative Examples as shown in Table 11-3 in both the test method and the evaluation criteria to evaluate hydrolytic resistance. The results are shown in Table 11-3.

11.7 Test Example 2

The same procedures as in Test Example 1 of Item 1.5 were carried out in the both test method and the evaluation criteria to evaluate low-temperature fixing ability, provided that the evaluation criteria are as follows. The results are shown in Table 11-3.

A: The lowest fixing temperature is less than 140° C.
B: The lowest fixing temperature is 140° C. or more and less than 160° C.
C: The lowest fixing temperature is 160° C. or more.

11.8 Test Example 3

Hot Offset Resistance

The same procedures as in Test Example 3 of Item 10.11 were carried out in both the test method and evaluation criteria to evaluate hydrolytic resistance. The results are shown in Table 11-3.

11.9 Test Example 4

Resistance to Background Fogging Under High-Temperature, High Humidity Conditions

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 11-3.

11.10 Test Example 5

A toner was loaded to “PAGEPRESTO N-4” (manufactured by CASIO COMPUTER CO., LTD., fixing: contact fixing method, nonmagnetic monocomponent development method, developer roller diameter: 2.3 cm) under the conditions of a temperature of 32° C. and humidity of 80%, and the steps up to transferring were carried out, and fixing was carried out with an external fixing device. A toner was loaded to this apparatus, and printing was carried out for 2,000 sheets. Thereafter, a solid image of a square having 2 cm each side was printed at a position 2 cm away from the top center of an A4 sheet (210 mm×297 mm), and background fogging was evaluated in accordance with the method shown below using the above A4 sheet.

(1) In a part where background fogging was generated by solid image printing at a position of additionally 2 cm below a distance corresponding to a circumference of a developer roller (7.2 cm) from the top center of the sheet, i.e. 9.2 cm from the top center, L* values, a* values, and b* values were determined at four (4) points taken along the sides of the square, 0.5 cm away from each of the four corners, within the square having 2 cm each side with a color-difference-meter “CR-321” (manufactured by Minolta), and an average for each value was calculated. (2) L* values, a* values, and b* values were determined at 4 points in the blank sheet portion at distances 4 cm and 8 cm to the left and to the right, away from the center located 10.2 cm away from the top end of the image in the same manner as in (1), and an average for each value was calculated.

A difference in the two values in (1) and (2) (ΔE) was obtained by the following formula, and the extent of the generation of background fogging was evaluated in accordance with the following evaluation criteria. The results are shown in Table 11-3.
ΔE=√{square root over ((L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²)}{square root over ((L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²)}{square root over ((L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²)} [Math 3]

wherein L₁*, a₁* and b₁* are each of the measurement values in the item (1), and each of L₂*, a₂* and b₂* are each of the measurement values in the item (2).

12.1 Production Example 1 of Resins

A: ΔE is less than 0.5.
B: ΔE is 0.5 or more and less than 1.
C: ΔE is 1 or more.

	TABLE 11-3

	Evaluation of Toner
							Resistance to
							Background
							Fogging under
							High-Temperature,
			Hydrolytic	Low-Temp.	Hot Offset	Storage	High-Humidity
No. 11-	Resin Binder*	D₅₀	Resistance	Fixing Ability	Resistance	Ability	Conditions

Ex. 1	Resin A	6.5	A	A	A	A	A
Ex. 2	Resin B	6.6	A	B	A	A	A
Ex. 3	Resin C	6.4	A	A	B	B	A
Ex. 4	Resin D	6.8	B	A	A	B	A
Ex. 5	Resin E	6.4	A	A	A	A	B
Ex. 6	Resin F	6.0	A	A	A	B	A
Ex. 7	Resin G	6.5	B	A	B	B	A
Ex. 8	Resin A/Resin C(50/50)	6.3	A	A	A	A	A
Ex. 9	Resin A/Resin G(50/50)	6.2	B	A	A	B	A
Ex. 10	Resin H/Resin C(50/50)	6.1	B	A	B	B	A
Ex. 11	Resin I/Resin C(50/50)	6.8	B	B	B	B	B
Ex. 12	Resin J/Resin C(50/50)	6.6	B	A	B	B	B
Ex. 13	Resin A	6.9	A	A	A	A	A
Comp.	Resin H	6.4	B	A	C	D	B
Ex. 1
Comp.	Resin I	6.8	D	C	C	B	C
Ex. 2
Comp.	Resin J	6.7	D	A	D	D	C
Ex. 3

*Inside the parenthesis shows a weight ratio of the resins.

It can be seen from the above results that as compared to the toners of Examples 11-1 to 11-13, the toner of Comparative Example 11-1 containing a polyester in which an aliphatic polyhydric alcohol other than an alcohol A is used is deficient in storage ability, while having a favorable low-temperature fixing ability. Also, the toner of Comparative Example 11-2 containing a polyester in which an alcohol A is not used, an aromatic polyhydric alcohol is used, but a succinic acid derivative is also not used, and the toner of Comparative Example 11-3 containing a polyester in which an aliphatic polyhydric alcohol other than an alcohol A is used and a succinic derivative is also not used are deficient in all of the properties.

Example 12

Resins A, B, D, F, G, I, and J

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers for a polyester other than trimellitic anhydride and an esterification catalyst, as listed in Table 12-1 or 12-2. The mixture was heated in a mantle heater to 180° C. in a nitrogen atmosphere, and then heated to 230° C. over 10 hours. Thereafter, having confirmed that a conversion rate at 230° C. reached 95% or higher, the reaction mixture was cooled to 160° C., and a mixed solution of raw material monomers for a styrenic resin, a dually reactive monomer and a polymerization initiator as listed in Table 12-1 or 12-2 was added dropwise thereto over 1 hour. Thereafter, the mixture was kept at 160° C. for 30 minutes, and heated to 210° C., and the heated mixture was subjected to a reaction at 8 kPa for 1 hour. Thereafter, trimellitic anhydride shown in Table 12-1 or 12-2 was added thereto, and the mixture was subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a hybrid resin. Here, the conversion rate refers to a value calculated by:
[amount of water generated in reaction(mol)/theoretical amount of generated water]×100.

12.2 Production Example 2 of Resin

12.3 Production Example 3 of Resin

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers for a polyester other than trimellitic anhydride, as listed in Table 12-1. The mixture was cooled in a mantle heater to 160° C. in a nitrogen atmosphere, and a mixed solution of raw material monomers for a styrenic resin, a dually reactive monomer and a polymerization initiator, as listed in Table 12-1 was added dropwise thereto over 1 hour. Thereafter, the mixture was kept at 160° C. for 30 minutes, then subjected with an esterification catalyst, heated to 180° C., and thereafter heated to 230° C. over 10 hours. Thereafter, having confirmed that a conversion rate at 230° C. reached 95% or higher, the reaction mixture was heated to 210° C., trimellitic anhydride shown in Table 12-1 was then added thereto, and the mixture was subjected to a reaction 40 kPa until a desired softening point was reached, to provide a hybrid resin.

Resin E

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers for a polyester other than trimellitic anhydride and an esterification catalyst, as listed in Table 12-1. The mixture was heated in a mantle heater to 180° C. in a nitrogen atmosphere, and then heated to 230° C. over 10 hours. Thereafter, having confirmed that a conversion rate at 230° C. reached 95% or higher, the reaction mixture was cooled to 160° C., and a wax was supplied thereto. Thereafter, a mixed solution of raw material monomers for a styrenic resin, a dually reactive monomer and a polymerization initiator as listed in Table 12-1 was added dropwise thereto over 1 hour. Thereafter, the mixture was kept at 160° C. for 30 minutes, and heated to 210° C., and the heated mixture was subjected to a reaction at 8 kPa for 1 hour. Thereafter, trimellitic anhydride shown in Table 12-1 was added thereto, and the mixture was subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a hybrid resin.

12.4 Production Example 4 of Resin

Resin H

A 5-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a reflux condenser, and a nitrogen inlet tube was charged with raw material monomers for a polyester other than fumaric acid and trimellitic anhydride and an esterification catalyst, as listed in Table 12-2. The mixture was heated in a mantle heater to 180° C. in a nitrogen atmosphere, and then heated to 230° C. over 10 hours. Thereafter, having confirmed that a conversion rate at 230° C. reached 95% or higher, the reaction mixture was cooled to 160° C., and a mixed solution of raw material monomers for a styrenic resin, a dually reactive monomer and a polymerization initiator as listed in Table 12-2 was added dropwise thereto over 1 hour. Thereafter, the mixture was kept at 160° C. for 30 minutes. trimellitic anhydride, fumaric acid and a polymerization inhibitor listed in Table 12-2 were supplied thereto, and the mixture was heated to 210° C. over 4 hours, and subjected to a reaction at 40 kPa until a desired softening point was reached, to provide a hybrid resin.

12.5 Production Example 5 of Resin

Resin K

12.6 Production Example 6 of Resin

Resin L

	TABLE 12-1

	Resin A	Resin B	Resin C	Resin D	Resin E
	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers for Polyester (PES)
Alcohol Component
2,3-Butanediol	675	7.5	1350	15	675	7.5	675	7.5	675	7.5
1,2-Propanediol	571	7.5	—	—	571	7.5	571	7.5	571	7.5
Carboxylic Acid Component
Terephthalic Acid	1743	10.5	—	—	1743	10.5	1743	10.5	1743	10.5
Isophthalic Acid	—	—	1743	10.5	—	—	—	—	—	—
Trimellitic Anhydride	432	2.25	432	2.25	432	2.25	432	2.25	432	2.25
Esterification Catalyst
Dibutyltin Oxide	—	—	17.6	—	—	—	—	—	—	—
Tin(II) 2-Ethylhexanoate	17.1	—	—	—	—	—	17.1	—	17.1	—
Titanium Compound¹⁾	—	—	—	—	17.1	—	—	—	—	—
Dually Reactive Monomer
Acrylic Acid	46.5	0.75	46.5	0.75	74.4	1.2	46.5	0.75	46.5	0.75
Raw Material Monomers for Styrenic Resin (St)
Styrene	718	—	718	—	1149	—	522	—	718	—
2-Ethylhexyl Acrylate	137	—	137	—	219	—	100	—	137	—
Polymerization Initiator
Dibutyl Peroxide	34	—	34	—	55	—	25	—	34	—
Wax
Paraffin Wax²⁾	—	—	—	—	—	—	—	—	214	—
Amount of Alcohol A Contained in Alcohol	50	100	50	50	50
Component (% by mol)
Alcohol A/(Raw Material Monomers Other Than	24.2	60.8	23.9	24.2	24.2
Alcohol A) × 100 (parts by weight)
Total Amount of PES/Total Amount of St	4	4	2.5	5.5	4
(weight ratio)
Softening Point (° C.)	113.4	130.8	114.8	109.7	105.4
Glass Transition Temperature (° C.)	61.6	67.8	58.1	60.7	55.4
Acid Value (mgKOH/g)	28.4	24.5	20.2	25.9	21.9

¹⁾Titanium Diisopropylate bis(Triethanoaminate)
²⁾HNP-9: manufactured by Nippon Seiro, melting point 70° C.

	TABLE 12-2

	Resin F	Resin G	Resin H	Resin I	Resin J
	Amount	Amount	Amount	Amount	Amount
	Used	Used	Used	Used	Used
	g	mol	g	mol	g	mol	g	mol	g	mol

Raw Material Monomers for Polyester (PES)
Alcohol Component
2,3-Butanediol	1080	12	1080	12	585	6.5	675	7.5	—	—
1,2-Propanediol	—	—	—	—	495	6.5	571	7.5	—	—
1,3-Propanediol	—	—	228	3	—	—	—	—	—	—
2,4-Hexanediol	354	3	—	—	—	—	—	—	—	—
Ethylene Glycol	—	—	—	—	—	—	—	—	465	7.5
Neopentyl Glycol	—	—	—	—	—	—	—	—	780	7.5
Carboxylic Acid Component
Alkenylsuccinic Anhydride A	804	3	—	—	—	—	402	1.5	804	3
Terephthalic Acid	1494	9	1743	10.5	1079	6.5	1494	9	1494	9
Fumaric Acid	—	—	—	—	302	1.8	—	—	—	—
Trimellitic Anhydride	432	2.25	432	2.25	374	1.95	432	2.25	432	2.25
Esterification Catalyst
Dibutyltin Oxide	—	—	17.4	—	—	—	—	—	—	—
Tin(II) 2-Ethylhexanoate	20.8	—	—	—	—	—	17.9	—	19.9	—
Titanium Compound¹⁾	—	—	—	—	17.5	—	—	—	—	—
Dually Reactive Monomer
Acrylic Acid	46.5	0.75	46.5	0.75	40.3	0.65	46.5	0.75	46.5	0.75
Raw Material Monomers for Styrenic Resin (St)
Styrene	874	—	718	—	952	—	751	—	835	—
2-Ethylhexyl Acrylate	167	—	137	—	181	—	143	—	159	—
Polymerization Initiator
Dibutyl Peroxide	42	—	34	—	45	—	36	—	40	—
Wax
HNP-9²⁾	—	—	—	—	—	—	—	—	248	—
Amount of Alcohol A Contained in Alcohol	100	80	50	50	0
Component (% by mol)
Alcohol A/(Raw Material Monomers Other	51.6	44.1	25.5	42.2	0
Than Alcohol A) × 100 (parts by weight)
Total Amount of PES/Total Amount of St	4	4	2.5	4	4
(weight ratio)
Softening Point (° C.)	107.7	105.6	110	118.9	105.9
Glass Transition Temperature (° C.)	56.4	57.3	61.1	59.3	55.9
Acid Value (mgKOH/g)	24	27.4	26.9	25.4	24.6

¹⁾Titanium Diisopropylate bis(Triethanolaminate)
²⁾HNP-9: manufactured by Nippon Seiro, melting point 70° C.

	TABLE 12-3

	Resin K	Resin L
	Amount	Amount
	Used	Used
	g	mol	g	mol

Raw Material Monomers for Polyester (PES)
Alcohol Component
Ethylene Glycol	—	—	558	5.4
Neopentyl Glycol	—	—	936	9
BPA-PO¹⁾	1225	3.5	—	—
BPA-EO²⁾	1138	3.5	—	—
Carboxylic Acid Component
Alkenylsuccinic Anhydride A	375	1.4	965	3.6
Terephthalic Acid	697	4.2	1793	10.8
Trimellitic Anhydride	202	1.05	518	2.7
Esterification Catalyst
Tin(II) 2-Ethylhexanoate	18.2	—	23.9	—
Softening Point (° C.)	108.9	107.4
Glass Transition Temperature (° C.)	60.4	56.7
Acid Value (mgKOH/g)	16.8	29.5

¹⁾Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane
²⁾Polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane

12.7 Examples 1 to 12 and Comparative Examples 1 to 3

Preparation of Resin Dispersion

A 5-liter vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube was charged with 600 g of a methyl ethyl ketone, and 200 g of a resin binder listed in Table 12-4 was added thereto at room temperature to dissolve. Ten grams of triethylamine was added to the resulting solution to neutralize the solution, and subsequently 2,000 g of ion-exchanged water was added thereto. Thereafter, methyl ethyl ketone was distilled off from the mixture at a stirring rate of 250 r/min at 50° C. or less under a reduced pressure, to provide a self-dispersible aqueous dispersion of resin particles (resin content: 9.6% by weight (on a solid basis)). Polyester particles (primary particles) dispersed in the resulting resin dispersion had an average particle size of 0.3 μm.

A mixture of 50 g of a paraffin wax (HNP0190, manufactured by Nippon Seiro, melting point: 85° C.), 5 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) and 200 g of ion-exchanged water was heated to 95° C., and the paraffin wax was dispersed with a homogenizer. Thereafter, the mixture was subjected to a dispersion treatment with a pressure jetting homogenizer, to provide a releasing agent dispersion in which the paraffin wax was dispersed in an average particle size of 550 nm.

Fifty grams of a charge control agent (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.), 5 g of a nonionic surfactant (EMULGEN 150, manufactured by KAO Corporation, polyoxyethylene lauryl ether, HLB: 18.4, cloud point: 100° C. or more) and 200 g of ion-exchanged water were mixed. The mixture was dispersed for 10 minutes using glass beads with a sand grinder, to prepare a charge control agent dispersion in which the charge control agent was dispersed in an average particle size of 500 nm. However, remnants of coarse particles in the dispersion were observed.

Four-hundred and ninety grams of a resin particle dispersion, 20 g of a colorant dispersion, 15 g of a releasing agent dispersion, 7 g of a charge control agent dispersion and 2 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) obtained were mixed in a round-shaped stainless steel flask with a homogenizer to disperse. Thereafter, the dispersion was heated to 48° C., while stirring the contents inside the flask in a heating oil bath. Further, after the dispersion was kept at 48° C. for 1 hour, it was confirmed that aggregated particles having an average particle size of 6.0 μm were formed.

Three grams of an anionic surfactant (PELEX SS-L, manufactured by KAO Corporation) was added to the aggregated particle dispersion in which the aggregated particles were formed, and thereafter the above-mentioned stainless steel flask was equipped with a reflux tube. The dispersion was heated to 80° C. at a rate of 5° C./min while continuously stirring, and kept thereat for 5 hours, to unify and fuse the aggregated particles. Thereafter, the unified particles was cooled, filtered, and sufficiently washed with ion-exchanged water and dried, to provide colored powder of fine resin particles. The resulting colored powder of fine resin particles had having a volume-median particle size (D₅₀) of 6.3 μm.

Preparation of Resin Dispersion

To 100 parts by weight of the resulting colored powder of fine resin particles was added 1.0 part by weight of a hydrophobic silica (TS530, manufactured by Wacker Chemicals, number-average particle size: 8 nm). The mixture was mixed with a Henschel mixer and subjected to an external addition treatment, to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.5 μm.

12.8 Example 13

One thousand and three-hundred grams of Resin A, 100 g of an anionic surfactant (NEOPELEX G-15, manufactured by KAO Corporation, sodium dodecylbenzenesulfonate (solid content 15% by weight)), 100 g of a nonionic surfactant (EMULGEN 430, manufactured by KAO Corporation, polyoxyethylene oleyl ether (EO=26 mol added), HLB: 16.2, cloud point: 100° C. or more) and 689 g of a 5% by weight aqueous potassium hydroxide solution were dispersed in the 5-liter stainless steel vessel at 25° C., while stirring with a paddle-shaped stirrer at rate of 200 r/min. The contents were stabilized at 95° C., and kept for 2 hours while stirring with a paddle-shaped stirrer at a rate of 200 r/min. Subsequently, deionized water was added dropwise thereto at a rate of 15 g/min, while stirring with a paddle-shaped stirrer at a rate of 200 r/m, totaling in an amount of 2845 g of the deionized water. During this time, the temperature of the system was kept at 95° C. After the system was cooled, the mixture was passed through a 150-mesh wire gauze (opening: 105 μm), to provide a resin dispersion containing fine resin particles. The resin particles (primary particles) in the resulting resin dispersion had an average particle size of 0.15 μm and a solid content of 31% by weight, and no resin component were remained on the wire gauze.

A mixture of 50 g of a paraffin wax (HNP0190, manufactured by Nippon Seiro, melting point: 85° C.), 5 g of a cationic surfactant (SANISOL B50, manufactured by KAO Corporation) and 200 g of ion-exchanged water was heated to 95° C., and the paraffin wax was dispersed with a homogenizer. Thereafter, the mixture was subjected to a dispersion treatment with a pressure jetting homogenizer, to provide a releasing agent dispersion in which the paraffin wax was dispersed in an average particle size of 550 nm.

Three grams of an anionic surfactant (PELEX SS-L, manufactured by KAO Corporation) was added to an aggregated particle dispersion in which the aggregated particles were formed, and thereafter the above-mentioned stainless steel flask was equipped with a reflux tube. The dispersion was heated to 80° C. at a rate of 5° C./min while continuously stirring, and kept for 5 hours, to unify and fuse the aggregated particles. Thereafter, the unified particles were cooled, filtered, and sufficiently washed with ion-exchanged water and dried, to provide colored powder of fine resin particles. The resulting colored powder of fine resin particles had a volume-median particle size (D₅₀) of 6.3 μm.

To 100 parts by weight of the resulting colored powder of fine resin particles was added 1.0 part by weight of a hydrophobic silica (TS530, manufactured by Wacker Chemicals, number-average particle size: 8 nm), and the mixture was mixed with a Henschel mixer and subjected to an external addition treatment, to provide a cyan toner. The resulting cyan toner had a volume-median particle size (D₅₀) of 6.9 μm.

12.9 Test Example 1

Hydrolytic Resistance

The same procedures as in Test Example 1 of Item 10.9 were carried out using a resin binder used in each of Examples and Comparative Examples as shown in Table 12-4 in both the test method and the evaluation criteria to evaluate hydrolytic resistance. The results are shown in Table 12-4.

12.10 Test Example 2

A: The lowest fixing temperature is less than 140° C.
B: The lowest fixing temperature is 140° C. or more and less than 160° C.
C: The lowest fixing temperature is 160° C. or more.

12.11 Test Example 3

Hot Offset Resistance

The same procedures as in Test Example 3 of Item 10.11 were carried out in both the test method and the evaluation criteria to evaluate hot offset resistance. The results are shown in Table 12-4.

12.12 Test Example 4

The same procedures as in Test Example 2 of Item 1.6 were carried out in both the test method and the evaluation criteria to evaluate storage ability. The results are shown in Table 12-4.

12.13 Test Example 5

Durability

A toner was loaded to a nonmagnetic monocomponent development device “Oki Microline 5400” (manufactured by Oki Data Corporation), and images of a diagonally striped pattern with a print coverage of 5.5% were subjected to durability test under the conditions of a temperature of 32° C. and humidity of 85%. During the course of printing, black solid images were printed out for every 500 sheets to check for any lines formed on fixed images. The number of sheet up to a point where the lines are visually observed on the fixed images is defined as the number of durably printed sheets, and durability was evaluated in accordance with the following evaluation criteria. The results are shown in Table 12-4.